Mixed surfactant system

ABSTRACT

Surfactant system mixtures of mid-chain branched primary alkyl sulfate surfactants useful in cleaning compositions, especially for lower water temperature applications, formulated with higher levels (above about 20%) of linear alkyl benzene sulfonate and low levels of cationic surfactants.

This application is a 371 of PCT/US98/21419, filed Oct. 9, 1998, whichclaims the benefit of No. 60/061,883, filed on Oct. 10, 1997.

FIELD OF THE INVENTION

The present invention relates to mixed surfactant systems useful inlaundry and cleaning compositions, especially granular and liquiddetergent compositions, comprising mid-chain branched primary alkylsulfate surfactants, alkyl benzene sulfonate surfactants and cationicsurfactants within select relative proportions.

BACKGROUND OF THE INVENTION

Conventional detersive surfactants comprise molecules having awater-solubilizing substituent (hydrophilic group) and an oleophilicsubstituent (hydrophobic group). Such surfactants typically comprisehydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide,polyoxyethylene, and the like, attached to an alkyl, alkenyl or alkarylhydrophobe usually containing from about 10 to about 20 carbon atoms.Accordingly, the manufacturer of such surfactants must have access to asource of hydrophobe groups to which the desired hydrophile can beattached by chemical means. The earliest source of hydrophobe groupscomprised the natural fats and oils, which were converted into soaps(i.e., carboxylate hydrophile) by saponification with base. Coconut oiland palm oil are still used to manufacture soap, as well as tomanufacture the alkyl sulfate (“AS”) class of surfactants. Otherhydrophobes are available from petrochemicals, including alkylatedbenzene which is used to manufacture alkyl benzene sulfonate surfactants(“LAS”).

More recently, it has been discovered that certain relatively long-chainalkyl sulfate compositions containing mid-chain branching are preferredfor use in laundry products, especially under cool or cold water washingconditions (e.g., 20° C.-5° C.). These mid-chain branched primary alkylsulfate surfactants, which provide a surfactant mixture that is higherin surfactancy and has better low temperature water solubility thanlinear alkyl sulfate, can be suitably combined with one or more othertraditional detergent surfactants (e.g., other primary alkyl sulfates;linear alkyl benzene sulfonates; alkyl ethoxylated sulfates; nonionicsurfactants; etc.) to provide improved surfactant systems. However, ithas been determined that such surfactant systems containing higherlevels of linear alkyl benzene sulfonates (higher than about 20% byweight of the mixture of alkyl benzene sulfonate and mid-chain branchedalkyl sulfate) are not optimized in cleaning performance.

It has been surprisingly determined that cleaning performance ofsurfactant systems comprising these mid-chain branched primary alkylsulfate surfactants having greater than 14.5 carbon atoms in combinationwith higher levels of linear alkyl benzene sulfonate surfactant can befurther improved by including low levels of cationic surfactant in thesesurfactant systems.

BACKGROUND ART

U.S. Pat. No. 3,480,556 to deWitt, et al., Nov. 25, 1969, EP 439,316,published by Jul. 31, 1991, and EP 684,300, published Nov. 29, 1995, EP439,316, and U.S. Pat. Nos. 5,245,072, 5,284,989, 5,026,933, 3,480,556and 4,870,038. R. G. Laughlin in “The Aqueous Phase Behavior ofSurfactants”. Academic Press, N.Y. (1994) p. 347. See also Finger etal., “Detergent alcohols—the effect of alcohol structure and molecularweight on surfactant properties”, J. Amer. Oil Chemists' Society, Vol.44, p. 525 (1967) and Technical Bulletin, Shell Chemical Co., SC:364-80, EP 342,917 A, Unilever, published Nov. 23, 1989 U.S. Pat. No.4,102,823 and GB 1,399,966, G.B. Patent 1,299,966, Matheson et al.,published Jul. 2, 1975, EP 401,462 A, assigned to Henkel, published Dec.12, 1990. See also K. R. Wormuth and S. Zushma, Langmuir, Vol. 7,(1991), pp 2048-2053, R. Varadaraj et al., J. Phys. Chem., Vol. 95,(1991), pp 1671, Varadaraj et al., J. Colloid and Interface Sci., Vol.140, (1990), pp 31-34, and Varadaraj et al., Langmuir, Vol. 6 (1990), pp1376-1378.

“Linear Guerbet” alcohols are available from Henkel, e.g., EUTANOL G-16.

See also: Surfactant Science Series, Marcel Dekker, N.Y. (variousvolumes include those entitled “Anionic Surfactants” and “SurfactantBiodegradation”, the latter by R. D. Swisher, Second Edition, publ. 1987as Vol. 18; see especially p.20-24 “Hydrophobic groups and theirsources”; pp 28-29 “Alcohols”, pp 34-35 “Primary Alkyl Sulfates” and pp35-36 “Secondary Alkyl Sulfates”); and CEH Marketing Research Report“Detergent Alcohols” by R. F. Modler et al., Chemical EconomicsHandbook, 1993, 609.5000-609.5002; Kirk Othmer's Encyclopedia ofChemical Technology, 4th Edition, Wiley, N.Y., 1991, “Alcohols, HigherAliphatic” in Vol. 1, pp 865-913 and references therein.

SUMMARY OF THE INVENTION

The present invention relates to cleaning compositions comprisingsurfactant systems which comprise:

(a) from about 80% to about 99% (preferably from about 85% to about 99%,more preferably from about 90% to about 99%, and most preferably fromabout 92% to about 98%) by weight of an anionic cosurfactant mixture ofmid-chain branched primary alkyl sulfates and linear alkyl benzenesulfonates, wherein said mixture comprises:

(i) from about 35% to about 80%, by weight of this anionic cosurfactantmixture, of mid-chain branched primary alkyl sulfates having theformula:

wherein the total number of carbon atoms in the branched primary alkylmoiety of this formula (including the R, R¹, and R² branching) is from14 to 20, and wherein further for this surfactant mixture the averagetotal number of carbon atoms in the branched primary alkyl moietieshaving the above formula is within the range of greater than 14.5 toabout 18 (preferably greater than 14.5 to about 17.5. more preferablyfrom about 15 to about 17); R, R¹, and R² are each independentlyselected from hydrogen and C₁-C₃ alkyl (preferably methyl), provided R,R¹, and R² are not all hydrogen and, when z is 1, at least R or R¹ isnot hydrogen; M is one or more cations; w is an integer from 0 to 13; xis an integer from 0 to 13; y is an integer from 0 to 13; z is aninteger of at least 1; and w+x+y+z is from 8 to 14 (preferably less thanabout 80% of the alkyl sulfates have a total of 18 carbon atoms in thealkyl chain); and

(ii) from about 20% to about 65%, by weight of this anionic cosurfactantmixture, of C₁₀-C₁₆ linear alkyl benzene sulfonate; and

(b) from about 1% to about 20% (preferably from about 1% to about 15%,more preferably from about 1% to about 10%, and most preferably fromabout 2% to about 8%) of one or more cationic cosurfactants, preferablyC₈-C₁₄ cationic cosurfactants.

These cleaning compositions preferably comprise from about 0.1% to about99.9% (preferably from about 1% to about 50%) by weight of thesurfactant system and from about 0.1% to about 99.9% (preferably fromabout 1% to about 50%) by weight of one or more cleaning compositionadjunct ingredients.

Preferably, these cleaning compositions comprise a mixture of mid-chainbranched primary alkyl sulfate surfactants, wherein said mixturecomprises at least about 5% by weight of two or more mid-chain branchedalkyl sulfates having the formula:

or mixtures thereof; wherein M represents one or more cations; a, b, d,and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 andwherein further

when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to8;

when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to9;

when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to10;

when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to11;

when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to12;

when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to13;

when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to14;

when d+e=8, d is an integer from 2 to 7 and b is an integer from 1 to 6;

when d+e=9, d is an integer from 2 to 8 and b is an integer from 1 to 7;

when d+e=10, d is an integer from 2 to 9 and b is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and b is an integer from 1 to9;

when d+e=12, d is an integer from 2 to 11 and b is an integer from 1 to10;

when d+e=13, d is an integer from 2 to 12 and b is an integer from 1 to11;

when d+e=14, d is an integer from 2 to 13 and b is an integer from 1 to12;

wherein for this surfactant mixture the average total number of carbonatoms in the branched primary alkyl moieties having the above formulasis within the range of greater than 14.5 to about 18.

Such compositions may include mid-chain branched alkyl sulfate compoundsof formula:

wherein: a and b are integers and a+b is 12 or 13, a is an integer from2 to 11, b is an integer from 1 to 10 and M is selected from sodium,potassium. ammonium and substituted ammonium. More preferred embodimentsof such compounds include an alkyl sulfate compound of said formulawherein M is selected from sodium, potassium and ammonium.

Other mid-chain branched alkyl sulfate compounds which may be includedhave the formula:

wherein:

d and e are integers and d+e is from 10 or 11; and wherein further

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

and M is selected from sodium, potassium, ammonium and substitutedammonium, more preferably sodium, potassium and ammonium, mostpreferably sodium.

The present invention also relates to a method for cleaning fabricscomprising contacting a fabric in need of cleaning with an aqueoussolution of a cleaning composition as described hereinbefore.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (°C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to surfactant mixtures comprisingmid-chain branched alkyl sulfate surfactants, linear alkyl benzenesulfonate surfactants and cationic surfactants, and to cleaningcompositions containing these surfactant systems. For purposes of thisinvention, it is to be recognized that other surfactants may optionallybe present in the surfactant system according to the present invention,such as nonionic surfactants (e.g., alkyl ethoxylates) and other anionicsurfactants (e.g., linear alkyl sulfates). Such optional surfactants aredescribed in more detail herein after. However, for purposes ofcalculating the relative amounts of the essential components of thepresent surfactant system mixtures, only the weight of these essentialcomponents in the surfactant system are considered.

Thus, the anionic cosurfactant mixture of the mid-chain branched primaryalkyl sulfates and linear alkyl benzene sulfonates comprises from about80% to about 99% (most preferably from about 92% to about 98%) by weightof the total weight of these essential surfactants plus the essentialcationic surfactant. (Any optional surfactants present are not includedin this total weight.) The essential cationic surfactant thereforecomprises from about 1% to about 20% (most preferably from about 2% toabout 8%) by weight of the total weight of the essential surfactants.

Further, the essential anionic surfactants are combined in selectproportions relative to each other. Relative to the total weight of onlythe essential mid-chain branched alkyl sulfate and the linear alkylbenzene sulfonate, the mid-chain branched alkyl sulfate is present inthe present invention compositions from about 35% to about 80%. Thelinear alkyl benzene sulfonate is present from about 20% to about 65% byweight of the total weight of the essential anionic surfactants.

Mid-chain Branched Alkyl Sulfate

The branched surfactant compositions comprise one or more, preferablytwo or more, mid-chain branched primary alkyl sulfate surfactants havingthe formula

The surfactant mixtures of the present invention comprise moleculeshaving a linear primary alkyl sulfate chain backbone (i.e., the longestlinear carbon chain which includes the sulfated carbon atom). Thesealkyl chain backbones comprise from 12 to 19 carbon atoms; and furtherthe molecules comprise a branched primary alkyl moiety having at least atotal of 14, but not more than 20, carbon atoms. In addition, thesurfactant mixture has an average total number of carbon atoms for thebranched primary alkyl moieties within the range of from greater than14.5 to about 18. Thus, the present invention mixtures comprise at leastone branched primary alkyl sulfate surfactant compound having a longestlinear carbon chain of not less than 12 carbon atoms or more than 19carbon atoms, and the total number of carbon atoms including branchingmust be at least 14, and further the average total number of carbonatoms for the branched primary alkyl chains is within the range ofgreater than 14.5 to about 18.

For example, a C16 total carbon primary alkyl sulfate surfactant having13 carbon atoms in the backbone must have 1, 2, or 3 branching units(i.e., R, R¹ and/or R²) whereby total number of carbon atoms in themolecule is at least 16. In this example, the C16 total carbonrequirement may be satisfied equally by having, for example. one propylbranching unit or three methyl branching units.

R, R¹, and R² are each independently selected from hydrogen and C₁-C₃alkyl (preferably hydrogen or C₁-C₂ alkyl, more preferably hydrogen ormethyl, and most preferably methyl), provided R, R¹, and R² are not allhydrogen. Further, when z is 1, at least R or R¹ is not hydrogen.

Although for the purposes of the present invention surfactantcompositions the above formula does not include molecules wherein theunits R, R¹, and R² are all hydrogen (i.e., linear non-branched primaryalkyl sulfates), it is to be recognized that the present inventioncompositions may still further comprise some amount of linear,non-branched primary alkyl sulfate. Further, this linear non-branchedprimary alkyl sulfate surfactant may be present as the result of theprocess used to manufacture the surfactant mixture having the requisiteone or more mid-chain branched primary alkyl sulfates according to thepresent invention, or for purposes of formulating detergent compositionssome amount of linear non-branched primary alkyl sulfate may be admixedinto the final product formulation.

Further it is to be similarly recognized that non-sulfated mid-chainbranched alcohol may comprise some amount of the present inventioncompositions. Such materials may be present as the result of incompletesulfation of the alcohol used to prepare the alkyl sulfate surfactant,or these alcohols may be separately added to the present inventiondetergent compositions along with a mid-chain branched alkyl sulfatesurfactant according to the present invention.

M is hydrogen or a salt forming cation depending upon the method ofsynthesis. Examples of salt forming cations are lithium, sodium,potassium, calciun, magnesium, quaternary alkyl amines having theformula

wherein R³, R⁴, R⁵ and R⁶ are independently hydrogen, C₁-C₂₂ alkylene,C₄-C₂₂ branched alkylene, C₁-C₆ alkanol, C₁-C₂₂ alkenylene, C₄-C₂₂branched alkenylene, and mixtures thereof. Preferred cations areammonium (R³, R⁴, R⁵ and R⁶ equal hydrogen), sodium, potassium, mono-,di-, and trialkanol ammonium, and mixtures thereof. The monoalkanolammonium compounds of the present invention have R³ equal to C₁-C₆alkanol R⁴, R⁵ and R⁶ equal to hydrogen; dialkanol ammonium compounds ofthe present invention have R³ and R⁴ equal to C₁-C₆ alkanol, R⁵ and R⁶equal to hydrogen; trialkanol ammonium compounds of the presentinvention have R³, R⁴ and R⁵ equal to C₁-C₆ alkanol, R⁶ equal tohydrogen. Preferred alkanol ammonium salts of the present invention arethe mono-, di- and tri-quaternary ammonium compounds having theformulas: H₃N⁺CH₂CH₂OH, H₂N⁺(CH₂CH₂OH)₂, HN⁺(CH₂CH₂OH)₃. Preferred M issodium, potassium and the C₂ alkanol ammonium salts listed above; mostpreferred is sodium.

Further regarding the above formula, w is an integer from 0 to 13; x isan integer from 0 to 13; y is an integer from 0 to 13; z is an integerof at least 1; and w+x+y+z is an integer from 8 to 14.

Certain points of branching (i.e., the location along the chain of theR, R¹, and/or R² moieties in the above formula) are preferred over otherpoints of branching along the backbone of the surfactant. The formulabelow illustrates the mid-chain branching range (i.e., where points ofbranching occur), preferred mid-chain branching range, and morepreferred mid-chain branching range for mono-methyl substituted linearalkyl sulfates of the present invention.

It should be noted that for the mono-methyl substituted surfactantsthese ranges exclude the two terminal carbon atoms of the chain and thetwo carbon atoms immediately adjacent to the sulfate group. Forsurfactant mixtures comprising two or more of R, R¹, or R², alkylbranching at the 2-carbon atom is within the scope of the presentinvention. Surfactants having chains longer than ethyl (i.e. C₃ alkylsubstitutents) on the 2-carbon atom, however, are less preferred.

The formula below illustrates the mid-chain branching range, preferredmid-chain branching range, and more preferred mid-chain branching rangefor di-methyl substituted linear alkyl sulfates of the presentinvention.

When di-alkyl substituted primary alkyl sulfates arc combined withmono-substituted mid-chain branched primary alkyl sulfates, the di-alkylsubstituted primary alkyl sulfates having one methyl substitution on the2-carbon position and another methyl substitution in the preferred rangeas indicated above, are within the present invention.

The preferred surfactant mixtures of the present invention have at least0.001%, more preferably at least 5%, most preferably at least 20% byweight, of the mixture one or more branched primary alkyl sulfateshaving the formula

wherein the total number of carbon atoms, including branching, is from15 to 18, and wherein further for this surfactant mixture the averagetotal number of carbon atoms in the branched primary alkyl moietieshaving the above formula is within the range of greater than 14.5 toabout 18; R¹ and R² are each independently hydrogen or C₁-C₃ alkyl; M isa water soluble cation; x is from 0 to 11; y is from 0 to 11; z is atleast 2; and x+y+z is from 9 to 13; provided R¹ and R² are not bothhydrogen. More preferred are compositions having at least 5% of themixture comprising one or more mid-chain branched primary alkyl sulfateswherein x+y is equal to 9 and z is at least 2.

Preferably, the mixtures of surfactant comprise at least 5% of a midchain branched primary alkyl sulfate having R¹ and R² independentlyhydrogen, methyl, provided R¹ and R² are not both hydrogen; x+y is equalto 8, 9, or 10 and z is at least 2. More preferably the mixtures ofsurfactant comprise at least 20% of a mid chain branched primary alkylsulfate having R¹ and R² independently hydrogen, methyl, provided R¹ andR² are not both hydrogen; x+y is equal to 8,9, or 10 and z is at least2.

Preferred detergent compositions according to the present invention, forexample one useful for laundering fabrics, comprise from about 0.001% toabout 99% of a mixture of mid-chain branched primary alkyl sulfatesurfactants, said mixture comprising at least about 5% by weight of twoor more mid-chain branched alkyl sulfates having the formula:

or mixtures thereof; wherein M represents one or more cations; a, b, d,and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 andwherein further

when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to8;

when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to9;

when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to10;

when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to11;

when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to12;

when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to13;

when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to14;

when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6;

when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7;

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to10;

when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to11;

when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to12;

wherein further for this surfactant mixture the average total number ofcarbon atoms in the branched primary alkyl moieties having the aboveformulas is within the range of greater than 14.5 to about 18.

Further, the present invention surfactant composition may comprise amixture of branched primary alkyl sulfates having the formula

wherein the total number of carbon atoms per molecule, includingbranching, is from 14 to 20, and wherein further for this surfactantmixture the average total number of carbon atoms in the branched primaryalkyl moieties having the above formula is within the range of greaterthan 14.5 to about 18; R, R¹, and R² are each independently selectedfrom hydrogen and C₁-C₃ alkyl, provided R, R¹, and R² are not allhydrogen; M is a water soluble cation; w is an integer from 0 to 13; xis an integer from 0 to 13; y is an integer from 0 to 13; z is aninteger of at least 1; and w+x+y+z is from 8 to 14; provided that whenR² is a C₁-C₃ alkyl the ratio of surfactants having z equal to 1 tosurfactants having z of 2 or greater is at least about 1:1, preferablyat least about 1:5, more preferably at least about 1:10, and mostpreferably at least about 1:100. Also preferred are surfactantcompositions, when R² is a C₁-C₃ alkyl, comprising less than about 20%,preferably less than 10%, more preferably less than 5%, most preferablyless than 1%, of branched primary alkyl sulfates having the aboveformula wherein z equals 1.

The present invention further relates to novel branched primary alkylsulfate surfactants having the formula

wherein R¹ and R² are each independently hydrogen or C₁-C₃ alkyl; M is awater soluble cation; x is an integer from 0 to 12; y is an integer from0 to 12; z is an integer of at least 2; and x+y+z is from 11 to 14;provided:

a) R¹ and R² are not both hydrogen;

b) when one R¹ or R² is hydrogen and the other R¹ or R² is methyl, thenx+y+z is not 12 or 13; and

c) when R¹ is hydrogen and R² is methyl, x+y is not 11 when z is 3, andx+y is not 9 when z is 5.

R¹ and R² units are selected independently from hydrogen or C₁-C₃ alkyl(preferably hydrogen or C₁-C₂ alkyl; more preferably hydrogen or methyl)provided R and R¹ are not both hydrogen. M is as defined hereinbefore.

For mid-chain branched primary alkyl sulfates of the present inventionhaving more than one alkyl branch chain, the alkyl chain backbonescomprise from 12 to 18 carbon atoms. The maximum number of carbons thatcomprise the mid-chain branched primary alkyl sulfates of the presentinvention, including all branches, is 20 carbon atoms.

Preferred novel mid-chain branched primary alkyl sulfate compounds havethe formula:

wherein: a and b are integers and a+b is 12 or 13, a is an integer from2 to 11, b is an integer from 1 to 10 and M is selected from sodium,potassium, ammonium and substituted ammonium. More preferred embodimentsof such compounds include an alkyl sulfate compound of said formulawherein M is selected from sodium, potassium and ammonium.

Also preferred novel mid-chain branched primary alkyl sulfate compoundshave the formula:

wherein:

d and e are integers and d+e is 10 or 11; and wherein further

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

and M is selected from sodium, potassium, ammonium and substitutedammonium, more preferably sodium, potassium and ammonium, mostpreferably sodium.

Preferred mono-methyl branched primary alkyl sulfates are selected fromthe group consisting of: 3-methyl pentadecanol sulfate, 4-methylpentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methylpentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methylpentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methylpentadecanol sulfate, 11-methyl pentadecanol sulfate, 12-methylpentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methylhexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanolsulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol sulfate,8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methylhexadecanol sulfate, 11-methyl hexadecanol sulfate, 12-methylhexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methylhexadecanol sulfate, and mixtures thereof.

Preferred di-methyl branched primary alkyl sulfates are selected fromthe group consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyltetradecanol sulfate, 2,5-methyl tetradecanol sulfate, 2,6-methyltetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2,8-methyltetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyltetradecanol sulfate, 2,11-methyl tetradecanol sulfate, 2,12-methyltetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methylpentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methylpentadecanol sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methylpentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methylpentadecanol sulfate, 2,11-methyl pentadecanol sulfate, 2,12-methylpentadecanol sulfate, 2,13-methyl pentadecanol sulfate, and mixturesthereof.

The following branched primary alkyl sulfates comprising 16 carbon atomsand having one branching unit are examples of preferred branchedsurfactants useful in the present invention compositions:

wherein M is preferably sodium.

The following branched primary alkyl sulfates comprising 17 carbon atomsand having two branching units are examples of preferred branchedsurfactants according to the present invention:

wherein M is preferably sodium.

Preparation of Mid-chain Branched Alkyl Sulfates

The following reaction scheme outlines a general approach to thepreparation of mid-chain branched primary alkyl sulfates of the presentinvention.

An alkyl halide is converted to a Grignard reagent and the Grignard isreacted with a haloketone. After conventional acid hydrolysis,acetylation and thermal elimination of acetic acid, an intermediateolefin is produced (not shown in the scheme) which is hydrogenatedforthwith using any convenient hydrogenation catalyst such as Pd/C.

This route is favorable over others in that the branch, in thisillustration a 5-methyl branch, is introduced early in the reactionsequence.

Formylation of the alkyl halide resulting from the first hydrogenationstep yields alcohol product, as shown in the scheme. This can besulfated using any convenient sulfating agent, e.g., chlorosulfonicacid, SO3/air, or oleum, to yield the final branched primary alkylsulfate surfactant. There is flexibility to extend the branching oneadditional carbon beyond that which is achieved by a single formylation.Such extension can, for example, be accomplished by reaction withethylene oxide. See “Grignard Reactions of Nonmetallic Substances”, M.S. Kharasch and O. Reinmuth, Prentice-Hall, N.Y., 1954; J. Org. Chem.,J. Cason and W. R. Winans, Vol. 15 (1950), pp 139-147; J. Org Chem., J.Cason et al., Vol. 13 (1948), pp 239-248; J. Org Chem., J. Cason et al.,Vol. 14 (1949), pp 147-154; and J. Org Chem., J. Cason et al., Vol. 15(1950), pp 135-138 all of which are incorporated herein by reference.

In variations of the above procedure, alternate haloketones or Grignardreagents may be used. PBr3 halogenation of the alcohol from formylationor ethoxylation can be used to accomplish an iterative chain extension.

The preferred mid-chained branched primary alkyl sulfates of the presentinvention can also be readily prepared as follows:

A conventional bromoalcohol is reacted with triphenylphosphine followedby sodium hydride, suitably in dimethylsulfoxide/tetrahydrofuran, toform a Wittig adduct. The Wittig adduct is reacted with an alpha methylketone, forming an internally unsaturated methyl-branched alcoholate.Hydrogenation followed by sulfation yields the desired mid-chainbranched primary alkyl sulfate. Although the Wittig approach does notallow the practitioner to extend the hydrocarbon chain, as in theGrignard sequence, the Wittig typically affords higher yields. SeeAgricultural and Biological Chemistry, M. Horiike et al., vol. 42(1978), pp 1963-1965 included herein by reference.

Any alternative synthetic procedure in accordance with the invention maybe used to prepare the branched primary alkyl sulfates. The mid-chainbranched primary alkyl sulfates may, in addition be synthesized orformulated in the presence of the conventional homologs, for example anyof those which may be formed in an industrial process which produces2-alkyl branching as a result of hydroformylation. Mid-chain branchedsurfactant mixtures of the present invention are routinely added toother known commercial alkyl sulfates contained in the final laundryproduct formulation.

In certain preferred embodiments of the surfactant mixtures of thepresent invention, especially those derived from fossil fuel sourcesinvolving commercial processes, comprise at least 1 mid-chain branchedprimary alkyl sulfate, preferably at least 2, more preferably at least5, most preferably at least 8.

Particularly suitable for preparation of certain surfactant mixtures ofthe present invention are “oxo” reactions wherein a branched chainolefin is subjected to catalytic isomerization and hydroformylationprior to sulfation. The preferred processes resulting in such mixturesutilize fossil fuels as the starting material feedstock. Preferredprocesses utilize Oxo reaction on linear olefins (alpha or internal)with a limited amount of branching. Suitable olefins may be made bydimerization of linear alpha or internal olefins, by controlledoligomerization of low molecular weight linear olefins, by skeletalrearrangement of detergent range olefins, by dehydrogenation/skeletalrearrangement of detergent range paraffins, or by Fischer-Tropschreaction. These reactions will in general be controlled to:

1) give a large proportion of olefins in the desired detergent range(while allowing for the addition of a carbon atom in the subsequent Oxoreaction),

2) produce a limited number of branches, preferably mid-chain,

3) produce C₁-C₃ branches, more preferably ethyl, most preferablymethyl,

4) limit or eliminate gem dialkyl branching i.e. to avoid formation ofquaternary carbon atoms.

The suitable olefins can undergo Oxo reaction to give primary alcoholseither directly or indirectly through the corresponding aldehydes. Whenan internal olefin is used, an Oxo catalyst is normally used which iscapable of prior pre-isomerization of internal olefins primarily toalpha olefins. While a separately catalyzed (i.e. non-Oxo) internal toalpha isomerization could be effected, this is optional. On the otherhand, if the olefin-forming step itself results directly in an alphaolefin (e.g. with high pressure Fischer-Tropsch olefins of detergentrange), then use of a non-isomerizing Oxo catalyst is not only possible,but preferred. The scheme below summaries this process.

The process described herein above gives the more preferred5-methyl-hexadecyl sulfate in higher yield than the less preferred2,4-dimethylpentadecyl sulfate. This mixture is desirable under themetes and bounds of the present invention in that each product comprisesat total of 17 carbon atoms with linear alkyl chains having at least 13carbon atoms.

The following examples provide methods for synthesizing variouscompounds useful in the present invention compositions.

EXAMPLE I Preparation of sodium 7-methylhexadecyl sulfate Synthesis of(6-hydroxyhexyl) triphenylphosphonium bromide

Into a 5 L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo-1-hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9 mol)and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5 L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5 L) at 10° C. Vacuumfiltration followed by washing with ethyl ether and drying in a vacuumoven at 50° C. for 2 hrs. gives 1140 g of the desired product as whitecrystals.

Synthesis of 7-methylhexadecene-1-ol

Into a dried 5 L, 3 neck round bottom flask fitted with mechanicalstirring, nitrogen inlet, dropping funnel, thermometer and nitrogenoutlet is added 70.2 g of 60% sodium hydride (1.76 mol) in mineral oil.The mineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500ml) is added to the flask and the mixture is heated to 70°C. until evolution of hydrogen stops. The reaction mixture is cooled toroom temperature followed by addition of 1 L of anhydroustetrahydrofuran. (6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g,1 mol) is slurried with warm anhydrous dimethyl sulfoxide (50° C., 500ml) and slowly added to the reaction mixture through the dropping funnelwhile keeping it at 25-30° C. The mixture is stirred for 30 minutes atroom temperature at which time 2-undecanone (187 g, 1.1 mol) is slowlyadded through a dropping funnel. Reaction is slightly exothermic andcooling is needed to maintain 25-30° C. The mixture is stirred for 18hr. and then poured into a 5 L beaker containing 1 L purified water withstirring. The oil phase (top) is allowed to separate out in a separatoryfunnel and the water phase is removed. The water phase is washed withhexanes (500 ml) and the organic phase is separated and combined withthe oil phase from the water wash. The organic mixture is then extractedwith water 3 times (500 ml each) followed by vacuum distillation tocollect the clear, oily product (132 g) at 140° C. and 1 mm Hg.

Hydrogenation of 7-methylhexadecene-1-ol

Into a 3 L rocking autoclave liner is added 7-methylhexadecene-1-ol (130g, 0.508 mol), methanol (300 ml) and platinum on carbon (10% by weight,35 g). The mixture is hydrogenated at 180° C. under 1200 psig ofhydrogen for 13 hrs., cooled and vacuum filtered thru Celite 545 withwashing of the Celite 545, suitably with methylene chloride. If needed,the filtration can be repeated to eliminate traces of Pt catalyst, andmagnesium sulfate can be used to dry the product. The solution ofproduct is concentrated on a rotary evaporator to obtain a clear oil(124 g).

Sulfation of 7-methylhexadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform (300 ml) and 7-methylhexadecanol (124 g, 0.484 mol).Chlorosulfonic acid (60 g, 0.509 mol) is slowly added to the stirredmixture while maintaining 25-30° C. temperature with a ice bath. OnceHCl evolution has stopped (1 hr.) slowly add sodium methoxide (25% inmethanol) while keeping temperature at 25-30° C. until an aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedhot ethanol (55° C., 2 L). The mixture is vacuum filtered immediately.The filtrate is concentrated to a slurry on a rotary evaporator, cooledand then poured into 2 L of ethyl ether. The mixture is chilled to 5°C., at which point crystallization occurs, and vacuum filtered. Thecrystals arc dried in a vacuum oven at 50 C. for 3 hrs. to obtain awhite solid (136 g, 92% active by cat SO₃ titration).

EXAMPLE II Synthesis of sodium 7-methylpentadecyl sulfate Synthesis of(6-hydroxyhexyl) Triphenylphosphonium Bromide

Into a 5 L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo-1-hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9 mol)and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5 L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5 L) at 10° C. Vacuumfiltration of the mixture followed by washing the white crystals withethyl ether and drying in a vacuum oven at 50° C. for 2 hrs. gives 1140g of the desired product.

Synthesis of 7-methylpentadecene-1-ol

Into a dried 5 L, 3 neck round bottom flask fitted with mechanicalstirring, nitrogen inlet, dropping funnel. thermometer and nitrogenoutlet is added 80 g of 60% sodium hydride (2.0 mol) in mineral oil. Themineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500 ml) is added to the flask and heated to 70° C. untilevolution of hydrogen stops. The reaction mixture is cooled to roomtemperature followed by addition of 1 L of anhydrous tetrahydrofuran.(6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g, 1 mol) isslurried with warm anhydrous dimethyl sulfoxide (50° C., 500 ml) andslowly added to the reaction mixture thru the dropping funnel whilekeeping the reaction at 25-30° C. The reaction is stirred for 30 minutesat room temperature at which time 2-decanone (171.9 g, 1.1 mol) isslowly added thru a dropping funnel. Reaction is slightly exothermic andcooling is needed to maintain 25-30° C. Mixture is stirred for 18 hrs.and then poured into a separatory funnel containing 600 ml of purifiedwater and 300 ml of hexanes. After shaking the oil phase (top) isallowed to separate out and the water phase is removed. The extractionsof the oil phase are continued using water until both phases are clear.The organic phase is collected, vacuum distilled and purified by liquidchromatography (90:10 hexanes:ethyl acetate, silica gel stationaryphase) to obtain a clear, oily product (119.1 g).

Hydrogenation of 7-methylpentadecene-1-ol

Into a 3 L rocking autoclave glass liner (Autoclave Engineers) is added7-Methylpentadecene-1-ol (122 g, 0.508 mol), methanol (300 ml) andplatinum on carbon (10% by weight, 40 g). The mixture is hydrogenated at180° C. under 1200 psig of hydrogen for 13 hrs., cooled and vacuumfiltered thru Celite 545 with washing of Celite 545 with methylenechloride. The organic mixture is still dark from platinum catalyst sothe filtration procedure is repeated with concentration on a rotaryevaporator; dilution is carried out with methylene chloride (500 ml) andmagnesium sulfate is added to dry product. Vacuum filter thru Celite 545and concentrate filtrate on a rotary evaporator to obtain a clear oil(119 g).

Sulfation of 7-methylpentadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform (300 ml) and 7-methylpentadecanol (119 g 0.496 mol).Chlorosulfonic acid (61.3 g, 0.52 mol) is slowly added to the stirredmixture while maintaining 25-30° C. temperature with an ice bath. OnceHCl evolution has stopped (1 hr.) slowly add sodium methoxide (25% inmethanol) while keeping temperature at 25-30° C. until a aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedmethanol (1 L) and 300 ml of 1-butanol. Vacuum filter off the inorganicsalt precipitate and remove methanol from the filtrate on a rotaryevaporator. Cool to room temperature, add 1 L of ethyl ether and letstand for 1 hour. The precipitate is collected by vacuum filtration. Theproduct is dried in a vacuum oven at 50° C. for 3 hrs. to obtain a whitesolid (82 g, 90% active by cat SO3 titration).

EXAMPLE III Synthesis of sodium 7-methylheptadecyl sulfate Synthesis of(6-Hydroxyhexyl) Triphenylphosphonium bromide

Into a 5 L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo-1-hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9 mol)and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5 L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5 L) at 10° C. Vacuumfiltration of the mixture followed by washing the white crystals withethyl ether and drying in a vacuum oven at 50° C. for 2 hrs. gives 1140g of the desired product.

Synthesis of 7-methylheptadecene-1-ol

Into a dried 5 L, 3 neck round bottom flask fined with mechanicalstirring, nitrogen inlet, dropping funnel, thermometer and nitrogenoutlet is added 80 g of 60% sodium hydride (2.0 mol) in mineral oil. Themineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500 ml) is added to the flask and heated to 70° C. untilevolution of hydrogen stops. The reaction mixture is cooled to roomtemperature followed by addition of 1 L of anhydrous tetrahydrofuran.(6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g, 1 mol) isslurried with warm anhydrous dimethyl sulfoxide (50° C., 500 ml) andslowly added to the reaction mixture thru the dropping funnel whilekeeping the reaction at 25-30° C. The reaction is stirred for 30 minutesat room temperature at which time 2-dodecanone (184.3 g, 1.1 mol) isslowly added thru a dropping funnel. Reaction is slightly exothermic andcooling is needed to maintain 25-30° C. Mixture is stirred for 18 hrs.and then poured into a separatory funnel containing 600 ml of purifiedwater and 300 ml of hexanes. After shaking the oil phase (top) isallowed to separate out and the water phase is removed which is cloudy.The extractions are continued using water until the water phase and theorganic phase become clear. The organic phase is collected and purifiedby liquid chromatography (mobile phase-hexanes, stationary phase-silicagel ) to obtain a clear, oily product (116 g). HNMR of the final product(in deuterium oxide) indicates a CH ² —OSO₃ ⁻ triplet at the 3.8 ppmresonance, CH ² —CH ² —OSO₃ ⁻ multiplet at the 1.5 ppm resonance, CH ²of the alkyl chain at the 0.9-1.3 ppm resonance and CH—CH ³ branch pointoverlapping the R—CH ² CH ³ terminal methyl group at the 0.8 ppmresonance.

Hydrogenation of 7-methylheptadecene-1-ol

Into a 3 L rocking autoclave glass liner (Autoclave Engineers) is added7-Methylheptadecene-1-ol (116 g, 0.433 mol), methanol (300 ml) andplatinum on carbon (10% by weight, 40 g). The mixture is hydrogenated at180° C. under 1200 psig of hydrogen for 13 hrs., cooled and vacuumfiltered thru Celite 545 with washing of Celite 545 with methylenechloride. Vacuum filter thru Celite 545 and concentrate filtrate on arotary evaporator to obtain a clear oil (108 g).

Sulfation of 7-methylheptadecanol

Into a dried 1 L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform (300 ml) and 7-Methylheptadecanol (102 g, 0.378 mol).Chlorosulfonic acid (46.7 g, 0.40 mol) is slowly added to the stirredmixture while maintaining 25-30° C. temperature with a ice bath. OnceHCl evolution has stopped (1 hr.) slowly add sodium methoxide (25% inmethanol) while keeping temperature at 25-30° C. until an aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedhot methanol (45° C., 1 L) to dissolve the branched sulfate followedimmediately by vacuum filtration to remove the inorganic saltprecipitate and repeated a second time. The filtrate is then cooled to5° C. at which time 1 L of ethyl ether is added and let stand for 1hour. The precipitate is collected by vacuum filtration. The product isdried in a vacuum oven at 50 C. for 3 hrs. to obtain a white solid (89g, 88% active by cat SO₃ titration). HNMR of the final product (indeuterium oxide) indicates a CH ² —OSO₃ ⁻ triplet at the 3.8 ppmresonance, CH ² —CH ² —OSO₃ ⁻ multiplet at the 1.5 ppm resonance, CH ²of the alkyl chain at the 0.9-1.3 ppm resonance and CH—CH ³ branch pointoverlapping the R—CH ² CH ³ terminal methyl group at the 0.8 ppmresonance. Mass spectrometry data shows a molecular ion peak with a massof 349.1 corresponding to the 7-methylheptadecyl sulfate ion. Also shownis the methyl branch at the 7 position due to the loss of 29 mass unitsat that position.

The following two analytical methods for characterizing branching in thepresent invention surfactant compositions are useful:

1) Separation and Identification of Components in Fatty Alcohols (priorto sulfation or after hydrolysis of alcohol sulfate for analyticalpurposes). The position and length of branching found in the precursorfatty alcohol materials is determined by GC/MS techniques [see: D. J.Harvey, Biomed, Environ. Mass Spectrom (1989). 18(9), 719-23; D. J.Harvey, J. M. Tiffany, J. Chromatogr. (1984), 301(1), 173-87; K. A.Karlsson, B. E. Samuelsson. G. O. Steen, Chem. Phys. Lipids (1973),11(1), 17-38].

2) Identification of Separated Fatty Alcohol Sulfate Components byMS/MS. The position and length of branching is also determinable by IonSpray-MS/MS or FAB-MS/MS techniques on previously isolated fatty alcoholsulfate components.

The average total carbon atoms of the branched primary alkyl sulfatesherein can be calculated from the hydroxyl value of the precursor fattyalcohol mix or from the hydroxyl value of the alcohols recovered byextraction after hydrolysis of the alcohol sulfate mix according tocommon procedures, such as outlined in “Bailey's Industrial Oil and FatProducts”, Volume 2, Fourth Edition, edited by Daniel Swern, pp.440-441.

Linear Alkyl Benzene Sulfonate

Linear alkyl benzene sulfonate surfactants are well known. They areanionic surfactants selected from the alkali metal salts of alkylbenzenesulfonic acids in which the alkyl group contains from about 10 to 16carbon atoms, in straight chain or branched chain configuration. (SeeU.S. Pat. Nos. 2,220,099 and 2,477,383, incorporated herein byreference.) Especially preferred are the sodium and potassium linearstraight chain alkylbenzene sulfonates (LAS) in which the average numberof carbon atoms in the alkyl group is from about 10 to 14. SodiumC₁₁-C₁₄ LAS is especially preferred.

Cationic Surfactants

Nonlimiting examples of cationic surfactants useful herein typically atlevels from about 0.1% to about 50%, by weight include the cholineester-type quats and alkoxylated quaternary ammonium (AQA) surfactantcompounds, and the like.

Cationic co-surfactants useful as a component of the surfactant systemis a cationic choline ester-type quat surfactant which are preferablywater dispersible compounds, more preferably water soluble, havingsurfactant properties and comprise at least one ester (i.e. —COO—)linkage and at least one cationically charged group. Suitable cationicester surfactants, including choline ester surfactants, have for examplebeen disclosed in U.S. Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.

Preferred cationic ester surfactants are those having the formula:

wherein R¹ is a C₅-C₃₁ linear or branched alkyl alkenyl or alkaryl chainor M⁻.N⁺(R₆R₇R₈)(CH₂)_(s); X and Y, independently, are selected from thegroup consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOOwherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOOgroup; R₂, R₃, R₄, R₆, R₇ and R₈ are independently selected from thegroup consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl andalkaryl groups having from 1 to 4 carbon atoms; and R₅ is independentlyH or a C₁-C₃ alkyl group; wherein the values of m, n, s and tindependently lie in the range of from 0 to 8, the value of b lies inthe range from 0 to 20, and the values of a, u and v independently areeither 0 or 1 with the proviso that at least one of u or v must be 1;and wherein M is a counter anion.

Preferably R₂, R₃ and R₄ are independently selected from CH₃and—CH₂CH₂OH.

Preferably M is selected from the group consisting of halide, methylsulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride,bromide or iodide.

Preferred water dispersible cationic ester surfactants are the cholineesters having the formula:

wherein R₁ is a C₁₁-C₁₉ linear or branched alkyl chain.

Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methylammonium halides (R¹=C₁₇ alkyl),palmitoyl choline ester quaternary methylammonium halides (R¹=C₁₅alkyl), myristoyl choline ester quaternary methylammonium halides(R¹=C₁₃ alkyl), lauroyl choline ester quaternary methylammonium halides(R¹=C₁₁ alkyl), cocoyl choline ester quaternary methylammonium halides(R¹=C₁₁-C₁₃ alkyl), tallowyl choline ester quaternary methylammoniumhalides (R¹=C₁₅-C₁₇ alkyl), and any mixtures thereof.

The particularly preferred choline esters, given above, may be preparedby the direct esterification of a fatty acid of the desired chain lengthwith dimethylaminoethanol, in the presence of an acid catalyst. Thereaction product is then quaternized with a methyl halide, preferably inthe presence of a solvent such as ethanol, propylene glycol orpreferably a fatty alcohol ethoxylate such as C₁₀-C₁₈ fatty alcoholethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groupsper mole forming the desired cationic material. They may also beprepared by the direct esterification of a long chain fatty acid of thedesired chain length together with 2-haloethanol, in the presence of anacid catalyst material. The reaction product is then quaternized withtrimethylamine, forming the desired cationic material.

Other suitable cationic ester surfactants have the structural formulasbelow, wherein d may be from 0 to 20.

In a preferred aspect these cationic ester surfactant are hydrolysableunder the conditions of a laundry wash method.

Cationic co-surfactants useful herein also include alkoxylatedquaternary ammonium (AQA) surfactant compounds (referred to hereinafteras “AQA compounds”) having the formula:

wherein R¹ is a linear or branched alkyl or alkenyl moiety containingfrom about 8 to about 18 carbon atoms, preferably 10 to about 16 carbonatoms, most preferably from about 10 to about 14 carbon atoms; R² is analkyl group containing from one to three carbon atoms, preferablymethyl; R³ and R⁴ can vary independently and are selected from hydrogen(preferred), methyl and ethyl; X⁻ is an anion such as chloride, bromide,methylsulfate, sulfate, or the like, sufficient to provide electricalneutrality. A and A′ can vary independently and are each selected fromC₁-C₄ alkoxy, especially ethoxy (i.e., —CH₂CH₂O—), propoxy, butoxy andmixed ethoxy/propoxy; p is from 0 to about 30, preferably 1 to about 4and q is from 0 to about 30, preferably 1 to about 4, and mostpreferably to about 4; preferably both p and q are 1. See also: EP2,084, published May 30, 1979, by The Procter & Gamble Company, whichdescribes cationic co-surfactants of this type which are also usefulherein.

AQA compounds wherein the hydrocarbyl substituent R¹ is C₈-C₁₁,especially C₁₀, enhance the rate of dissolution of laundry granules,especially under cold water conditions, as compared with the higherchain length materials. Accordingly, the C₈-C₁₁ AQA surfactants may bepreferred by some formulators. The levels of the AQA surfactants used toprepare finished laundry detergent compositions can range from about0.1% to about 5%. typically from about 0.45% to about 2.5%, by weight.

According to the foregoing, the following are nonlimiting, specificillustrations of AQA surfactants used herein. It is to be understoodthat the degree of alkoxylation noted herein for the AQA surfactants isreported as an average, following common practice for conventionalethoxylated nonionic surfactants. This is because the ethoxylationreactions typically yield mixtures of materials with differing degreesof ethoxylation. Thus, it is not uncommon to report total EO valuesother than as whole numbers, e.g., “EO2.5”, “EO3.5”, and the like.

Designation R¹ R² ApR³ A′qR⁴ AQA-1 C₁₂-C₁₄ CH₃ EO EO (also referred toas Coco Methyl EO2) AQA-2 C₁₂-C₁₆ CH₃ (EO)₂ EO AQA-3 C₁₂-C₁₄ CH₃ (EO)₂(EO)₂ (Coco Methyl EO4) AQA-4 C₁₂ CH₃ EO EO AQA-5 C₁₂-C₁₄ CH₃ (EO)₂(EO)₃ AQA-6 C₁₂-C₁₄ CH₃ (EO)₂ (EO)₃ AQA-7 C₈-C₁₈ CH₃ (EO)₃ (EO)₂ AQA-8C₁₂-C₁₄ CH₃ (EO)₄ (EO)₄ AQA-9 C₁₂-C₁₄ C₂H₅ (EO)₃ (EO)₃ AQA-10 C₁₂-C₁₈C₃H₇ (EO)₃ (EO)₄ AQA-11 C₁₂-C₁₈ CH₃ (propoxy) (EO)₃ AQA-12 C₁₀-C₁₈ C₂H₅(iso-propoxy)₂ (EO)₃ AQA-13 C₁₀-C₁₈ CH₃ (EO/PO)₂ (EO)₃ AQA-14 C₈-C₁₈ CH₃(EO)₁₅* (EO)₁₅* AQA-15 C₁₀ CH₃ EO EO AQA-16 C₈-C₁₂ CH₃ EO EO AQA-17C₉-C₁₁ CH₃ EO 3.5 Avg. AQA-18 C₁₂ CH₃ EO 3.5 Avg. AQA-19 C₈-C₁₄ CH₃(EO)₁₀ (EO)₁₀ AQA-20 C₁₀ C₂H₅ (EO)₂ (EO)₃ AQA-21 C₁₂-C₁₄ C₂H₅ (EO)₅(EO)₃ AQA-22 C₁₂-C₁₈ C₃H₇ Bu (EO)₂ *Ethoxy, optionally end-capped withmethyl or ethyl.

The preferred bis-ethoxylated cationic surfactants herein are availableunder the trade name ETHOQUAD from Akzo Nobel Chemicals Company.

Highly preferred bis-AQA compounds for use herein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, preferably C₁₀,C₁₂, C₁₄ alkyl and mixtures thereof, and X is any convenient anion toprovide charge balance, preferably chloride. With reference to thegeneral AQA structure noted above, since in a preferred compound R¹ isderived from coconut (C₁₂-C₁₄ alkyl) fraction fatty acids, R² is methyland ApR³ and A′qR⁴ are each monoethoxy, this preferred type of compoundis referred to herein as “CocoMeEO2” or “AQA-1” in the above list.

Other preferred AQA compounds herein include compounds of the formula:

wherein R¹ is C₁₀-C₁₈ hydrocarbyl, preferably C₁₀-C₁₄ alkyl,independently p is 1 to about 3 and q is 1 to about 3, R² is C₁-C₃alkyl, preferably methyl, and X is an anion, especially chloride.

Other compounds of the foregoing, type include those wherein the ethoxy(CH₂CH₂O) units (EO) are replaced by butoxy (Bu), isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

Additional cationic co-surfactants are described. for example, in the“Surfactant Science Series, Volume 4, Cationic Surfactants” or in the“Industrial Surfactants Handbook”. Classes of useful cationicsurfactants described in these references include amide quats (i.e.,Lexquat AMG & Schercoquat CAS), glycidyl ether quats (i.e., Cyostat609), hydroxyalkyl quats (i.e., Dehyquart E), alkoxypropyl quats (i.e.,Tomah Q-17-2), polypropoxy quats (Emcol CC-9), cyclic alkylammoniumcompounds (i.e., pyridinium or imidazolinium quats), and/or benzalkoniumquats.

It is to be noted that formulation of the present invention compositionsmay involve simple admixing of the surfactant ingredients or pre-forminga complex of these cationic cosurfactants with one or more of theanionic surfactants, as well as any other methods of forming thesurfactant systems.

The following illustrates various other adjunct ingredients which may beused in the compositions of this invention, but is not intended to belimiting thereof. While the combination of the surfactant system withsuch adjunct compositional ingredients can be provided as finishedproducts in the form of liquids, gels, bars, or the like usingconventional techniques, the manufacture of the granular laundrydetergents herein requires some special processing techniques in orderto achieve optimal performance. Accordingly, the manufacture of laundrygranules will be described hereinafter separately in the GranulesManufacture section (below), for the convenience of the formulator.

Industrial Applicability

Surfactant systems of the type herein can be used in all manner ofcleaning compositions. The detergent compositions of the invention thusmay also contain additional detergent components. The precise nature ofthese additional components, and levels of incorporation thereof willdepend on the physical form of the composition, and the precise natureof the cleaning operation for which it is to be used. The longer-chainmid-chain branched derivatives are more soluble than expected and theshorter-chain derivatives clean better than expected. Cleaningcompositions herein include, but are not limited to: granular, bar-formand liquid laundry detergents; liquid hand dishwashing compositions;liquid, gel and bar-form personal cleansing products; shampoos;dentifrices; hard surface cleaners, and the like. Such compositions cancontain a variety of conventional detersive ingredients.

The following listing of such ingredients is for the convenience of theformulator, and not by way of limitation of the types of ingredientswhich can be used with the branched-chain surfactants herein. Thecompositions of the invention preferably contain one or more additionaldetergent components selected from surfactants, builders, alkalinitysystem, organic polymeric compounds, suds suppressors, soil suspensionand anti-redeposition agents and corrosion inhibitors.

Bleaching Compounds—Bleaching Agents and Bleach Activators—The detergentcompositions herein preferably further contain bleaching agents orbleaching compositions containing a bleaching agent and one or morebleach activators. Bleaching agents will typically be at levels of fromabout 1% to about 30%, more typically from about 5% to about 20%, of thedetergent composition, especially for fabric laundering. If present, theamount of bleach activators will typically be from about 0.1% to about60%, more typically from about 0.5% to about 40% of the bleachingcomposition comprising the bleaching agent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.These include oxygen bleaches as well as other bleaching agents.Perborate bleaches, e.g., sodium perborate (e.g., mono- ortetra-hydrate) can be used herein.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patentapplication Ser. No. 740,446, Burns et al, filed Jun. 3, 1985, EuropeanPatent Application 0,133,354, Banks et al, published Feb. 20, 1985, andU.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 toBurns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent “percarbonate” bleaches, sodium pyrophosphate peroxyhydrate,urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1.250 micrometers.Optionally, the percarbonate can be coated with silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators, which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. Various nonlimitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, issuedApr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. Thenonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators are typical, and mixtures thereof can also be used.See also U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Highly preferred amido-derived bleach activators are those of theformulae:

R¹N(R⁵)C(O)R²C(O)L

or

R¹C(O)N(R⁵)R²C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamido-caproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesul-fonate,(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof asdescribed in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is:

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae:

wherein R⁶ is H or an alkyl, aryl, alkoxyaryl, or alkaryl groupcontaining from 1 to about 12 carbon atoms. Highly preferred lactamactivators include benzoyl caprolactam, octanoyl caprolactam,3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoylcaprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoylvalerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8, 1985,incorporated herein by reference, which discloses acyl caprolactams,including benzoyl caprolactam, adsorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from about 0.025% to about1.25%, by weight, of such bleaches, especially sulfonate zincphthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. Nos. 5,246,621, 5,244,594; 5,194,416; 5,114,606; and European Pat.App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferredexamples of these catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(PF₆)₂, Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), andmixtures thereof. Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following U.S. Pat. Nos.: 4,728,455; 5,284,944;5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from about 0.1 ppmto about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in M. L. Tobe, “Base Hydrolysis of Transition-Metal Complexes”,Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferredcobalt catalyst useful herein are cobalt pentaamine acetate salts havingthe formula [Co(NH₃)₅OAc] T_(y), wherein “OAc” represents an acetatemoiety and “T_(y)” is an anion, and especially cobalt pentaamine acetatechloride, [Co(NH₃)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)₂;[Co(NH₃)₅OAc](PF₆)₂; [Co(NH₃)₅OAc](SO₄); [Co(NH₃)₅OAc](BF₄)₂; and[Co(NH₃)₅OAc](NO₃)₂ (herein “PAC”).

These cobalt catalysts are readily prepared by known procedures, such astaught for example in the Tobe article and the references cited therein,in U.S. Pat. No. 4,810,410, to Diakun et al, issued Mar. 7, 1989, J.Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterizationof Inorganic Compounds, W. L. Jolly (Prentice-Hall; 1970), pp. 461-3;Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982);Inorg. Chem. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); andJournal of Physical Chemistry, 56, 22-25 (1952).

As a practical matter, and not by way of limitation, the compositionsand cleaning processes herein can be adjusted to provide on the order ofat least one part per hundred million of the active bleach catalystspecies in the aqueous washing medium, and will preferably provide fromabout 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm toabout 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, ofthe bleach catalyst species in the wash liquor. In order to obtain suchlevels in the wash liquor of an automatic washing process, typicalcompositions herein will comprise from about 0.0005% to about 0.2%, morepreferably from about 0.004% to about 0.08%, of bleach catalyst,especially manganese or cobalt catalysts, by weight of the cleaningcompositions.

Enzymes—Enzymes are preferably included in the present detergentcompositions for a variety of purposes, including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains fromsubstrates, for the prevention of refugee dye transfer in fabriclaundering, and for fabric restoration. Suitable enzymes includeproteases, amylases, lipases, cellulases, peroxidases, and mixturesthereof of any suitable origin, such as vegetable, animal, bacterial,fungal and yeast origin. Preferred selections are influenced by factorssuch as pH-activity and/or stability optima, thermostability, andstability to active detergents, builders and the like. In this respectbacterial or fungal enzymes are preferred, such as bacterial amylasesand proteases, and fungal cellulases.

“Detersive enzyme”, as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry, hard surfacecleaning or personal care detergent composition. Preferred detersiveenzymes are hydrolases such as proteases, amylases and lipases.Preferred enzymes for laundry purposes include, but are not limited to,proteases, cellulases, lipases and peroxidases. Highly preferred forautomatic dishwashing are amylases and/or proteases, including bothcurrent commercially available types and improved types which, thoughmore and more bleach compatible though successive improvements, have aremaining degree of bleach deactivation susceptibility.

Enzymes are normally incorporated into detergent or detergent additivecompositions at levels sufficient to provide a “cleaning-effectiveamount”. The term “cleaning effective amount” refers to any amountcapable of producing a cleaning, stain removal, soil removal, whitening,deodorizing, or freshness improving effect on substrates such asfabrics, dishware and the like. In practical terms for currentcommercial preparations, typical amounts are up to about 5 mg by weight,more typically 0.01 mg to 3 mg, of active enzyme per gram of thedetergent composition. Stated otherwise, the compositions herein willtypically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of acommercial enzyme preparation. Protease enzymes are usually present insuch commercial preparations at levels sufficient to provide from 0.005to 0.1 Anson units (AU) of activity per gram of composition. For certaindetergents, such as in automatic dishwashing, it may be desirable toincrease the active enzyme content of the commercial preparation inorder to minimize the total amount of non-catalytically active materialsand thereby improve spotting/filming or other end-results. Higher activelevels may also be desirable in highly concentrated detergentformulations.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble. When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as“Protease D” is a carbonyl hydrolase variant having an amino acidsequence not found in nature, which is derived from a precursor carbonylhydrolase by substituting a different amino acid for a plurality ofamino acid residues at a position in said carbonyl hydrolase equivalentto position +76, preferably also in combination with one or more aminoacid residue positions equivalent to those selected from the groupconsisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126,+128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218,+222, +260, +265, and/or +274 according to the numbering of Bacillusamyloliquefaciens subtilisin, as described in WO 95/10615 published Apr.20, 1995 by Genencor International.

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company, WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Amylases suitable herein, especially for, but not limited to automaticdishwashing purposes, include, for example. α-amylases described in GB1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. andTERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful. Engineeringof enzymes for improved stability, e.g., oxidative stability, is known.See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp.6518-6521. Certain preferred embodiments of the present compositions canmake use of amylases having improved stability in detergents such asautomatic dishwashing types, especially improved oxidative stability asmeasured against a reference-point of TERMAMYL® in commercial use in1993. These preferred amylases herein share the characteristic of being“stability-enhanced” amylases, characterized, at a minimum, by ameasurable improvement in one or more of: oxidative stability, e.g., tohydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH9-10; thermal stability, e.g., at common wash temperatures such as about60° C.; or alkaline stability, e.g., at a pH from about 8 to about 11,measured versus the above-identified reference-point amylase. Stabilitycan be measured using any of the art-disclosed technical tests. See, forexample, references disclosed in WO 9402597. Stability-enhanced amylasescan be obtained from Novo or from Genencor International. One class ofhighly preferred amylases herein have the commonality of being derivedusing site-directed mutagenesis from one or more of the Bacillusamylases, especially the Bacillus α-amylases, regardless of whether one,two or multiple amylase strains are the immediate precursors. Oxidativestability-enhanced amylases vs. the above-identified reference amylaseare preferred for use, especially in bleaching, more preferably oxygenbleaching, as distinct from chlorine bleaching, detergent compositionsherein. Such preferred amylases include (a) an amylase according to thehereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as furtherillustrated by a mutant in which substitution is made, using alanine orthreonine, preferably threonine, of the methionine residue located inposition 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®,or the homologous position variation of a similar parent amylase, suchas B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)stability-enhanced amylases as described by Genencor International in apaper entitled “Oxidatively Resistant alpha-Amylases” presented at the207th American Chemical Society National Meeting, Mar. 13-17 1994, by C.Mitchinson. Therein it was noted that bleaches in automatic dishwashingdetergents inactivate alpha-amylases but that improved oxidativestability amylases have been made by Genencor from B. licheniformisNCIB8061. Methionine (Met) was identified as the most likely residue tobe modified. Met was substituted, one at a time, in positions 8, 15,197, 256, 304, 366 and 438 leading to specific mutants, particularlyimportant being M197 L and M197T with the M197T variant being the moststable expressed variant. Stability was measured in CASCADE® andSUNLIGHT®; (c) particularly preferred amylases herein include amylasevariants having additional modification in the immediate parent asdescribed in WO 9510603 A and are available from the assignee, Novo, asDURAMYL®. Other particularly preferred oxidative stability enhancedamylase include those described in WO 9418314 to Genencor Internationaland WO 9402597 to Novo. Any other oxidative stability-enhanced amylasecan be used, for example as derived by site-directed mutagenesis fromknown chimeric, hybrid or simple mutant parent forms of availableamylases. Other preferred enzyme modifications are accessible. See WO9509909 A to Novo.

Other amylase enzymes include those described in WO 95/26397 and inco-pending application by Novo Nordisk PCT/DK96/00056. Specific amylaseenzymes for use in the detergent compositions of the present inventioninclude α-amylases characterized by having a specific activity at least25% higher than the specific activity of Termamyl® at a temperaturerange of 25° C. to 55° C. and at a pH value in the range of 8 to 10,measured by the Phadebas® α-amylase activity assay. (Such Phadebas®α-amylase activity assay is described at pages 9-10, WO 95/26397.) Alsoincluded herein are α-amylases which are at least 80% homologous withthe amino acid sequences shown in the SEQ ID listings in the references.These enzymes are preferably incorporated into laundry detergentcompositions at a level from 0.00018% to 0.060% pure enzyme by weight ofthe total composition, more preferably from 0.00024% to 0.048% pureenzyme by weight of the total composition.

Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307, Barbesgoard et al, Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® andCELLUZYME®(Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487, laid open Feb. 24, 1978. This lipase isavailable from Amano Pharmaceutical Co. Ltd., Nagoya, Japan. under thetrade name Lipase P “Amano,” or “Amano-P.” Other suitable commerciallipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,Tagata, Japan; Chromobacter viscosum lipases from U.S. BiochemicalCorp., U.S.A. and Disoynth Co., The Netherlands, and lipases exPseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosaand commercially available from Novo, see also EP 341,947, is apreferred lipase for use herein. Lipase and amylase variants stabilizedagainst peroxidase enzymes are described in WO 9414951 A to Novo. Seealso WO 9205249 and RD 94359044.

In spite of the large number of publications on lipase enzymes, only thelipase derived from Humicola lanuginosa and produced in Aspergillusoryzae as host has so far found widespread application as additive forfabric washing products. It is available from Novo Nordisk under thetradename Lipolase™, as noted above. In order to optimize the stainremoval performance of Lipolase, Novo Nordisk have made a number ofvariants. As described in WO 92/05249, the D96L variant of the nativeHumicola lanuginosa lipase improves the lard stain removal efficiency bya factor 4.4 over the wild-type lipase (enzymes compared in an amountranging from 0.075 to 2.5 mg protein per liter). Research Disclosure No.35944 published on Mar. 10, 1994, by Novo Nordisk discloses that thelipase variant (D96L) may be added in an amount corresponding to0.001-100-mg (5-500,000 LU/liter) lipase variant per liter of washliquor. The present invention provides the benefit of improved whitenessmaintenance on fabrics using low levels of D96L variant in detergentcompositions containing the mid-chain branched primary alkyl sulfatesurfactants in the manner disclosed herein, especially when the D96L isused at levels in the range of about 50 LU to about 8500 LU per liter ofwash solution.

Cutinase enzymes suitable for use herein are described in WO 8809367 Ato Genencor.

Peroxidase enzymes may be used in combination with oxygen sources. e.g.,percarbonate, perborate, hydrogen peroxide, etc., for “solutionbleaching” or prevention of transfer of dyes or pigments removed fromsubstrates during the wash to other substrates present in the washsolution. Known peroxidases include horseradish peroxidase, ligninase,and haloperoxidases such as chloro- or bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed in WO89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo.

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 A andWO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and inU.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials usefulfor liquid detergent formulations, and their incorporation into suchformulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al. Apr.14. 1981. Enzymes for use in detergents can be stabilized by varioustechniques. Enzyme stabilization techniques are disclosed andexemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP199,405 and EP 200,586. Oct. 29, 1986, Venegas. Enzyme stabilizationsystems are also described, for example, in U.S. Pat. No. 3,519,570. Auseful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, isdescribed in WO 9401532 A to Novo.

Enzyme Stabilizing System—The enzyme-containing compositions herein mayoptionally also comprise from about 0.001% to about 10%, preferably fromabout 0.005% to about 8%, most preferably from about 0.01% to about 6%,by weight of an enzyme stabilizing system. The enzyme stabilizing systemcan be any stabilizing system which is compatible with the detersiveenzyme. Such a system may be inherently provided by other formulationactives, or be added separately, e.g., by the formulator or by amanufacturer of detergent-ready enzymes. Such stabilizing systems can,for example, comprise calcium ion, boric acid, propylene glycol, shortchain carboxylic acids, boronic acids, and mixtures thereof, and aredesigned to address different stabilization problems depending on thetype and physical form of the detergent composition.

One stabilizing approach is the use of water-soluble sources of calciumand/or magnesium ions in the finished compositions which provide suchions to the enzymes. Calcium ions are generally more effective thanmagnesium ions and are preferred herein if only one type of cation isbeing used. Typical detergent compositions, especially liquids, willcomprise from about 1 to about 30, preferably from about 2 to about 20,more preferably from about 8 to about 12 millimoles of calcium ion perliter of finished detergent composition, though variation is possibledepending on factors including the multiplicity, type and levels ofenzymes incorporated. Preferably water-soluble calcium or magnesiumsalts are employed, including for example calcium chloride, calciumhydroxide, calcium formate, calcium malate, calcium maleate, calciumhydroxide and calcium acetate; more generally, calcium sulfate ormagnesium salts corresponding to the exemplified calcium salts may beused. Further increased levels of Calcium and/or Magnesium may of coursebe useful, for example for promoting the grease-cutting action ofcertain types of surfactant.

Another stabilizing approach is by use of borate species. See Severson,U.S. Pat. No. 4,537,706. Borate stabilizers, when used, may be at levelsof up to 10% or more of the composition though more typically, levels ofup to about 3% by weight of boric acid or other borate compounds such asborax or orthoborate are suitable for liquid detergent use. Substitutedboric acids such as phenylboronic acid, butaneboronic acid,p-bromophenylboronic acid or the like can be used in place of boric acidand reduced levels of total boron in detergent compositions may bepossible though the use of such substituted boron derivatives.

Stabilizing systems of certain cleaning compositions, for exampleautomatic dishwashing compositions, may further comprise from 0 to about10%, preferably from about 0.01% to about 6% by weight, of chlorinebleach scavengers, added to prevent chlorine bleach species present inmany water supplies from attacking and inactivating the enzymes,especially under alkaline conditions. While chlorine levels in water maybe small, typically in the range from about 0.5 ppm to about 1.75 ppm,the available chlorine in the total volume of water that comes incontact with the enzyme, for example during dish- or fabric-washing, canbe relatively large; accordingly, enzyme stability to chlorine in-use issometimes problematic. Since perborate or percarbonate, which have theability to react with chlorine bleach, may present in certain of theinstant compositions in amounts accounted for separately from thestabilizing system, the use of additional stabilizers against chlorine,may, most generally, not be essential, though improved results may beobtainable from their use. Suitable chlorine scavenger anions are widelyknown and readily available, and, if used, can be salts containingammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate,iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organicamines such as ethylenediaminetetracetic acid (EDTA) or alkali metalsalt thereof, monoethanolamine (MEA), and mixtures thereof can likewisebe used. Likewise, special enzyme inhibition systems can be incorporatedsuch that different enzymes have maximum compatibility. Otherconventional scavengers such as bisulfate, nitrate, chloride, sources ofhydrogen peroxide such as sodium perborate tetrahydrate, sodiumperborate monohydrate and sodium percarbonate, as well as phosphate,condensed phosphate, acetate, benzoate, citrate, formate, lactate,malate, tartrate, salicylate, etc., and mixtures thereof can be used ifdesired. In general, since the chlorine scavenger function can beperformed by ingredients separately listed under better recognizedfunctions, (e.g., hydrogen peroxide sources), there is no absoluterequirement to add a separate chlorine scavenger unless a compoundperforming that function to the desired extent is absent from anenzyme-containing embodiment of the invention; even then, the scavengeris added only for optimum results. Moreover, the formulator willexercise a chemist's normal skill in avoiding the use of any enzymescavenger or stabilizer which is majorly incompatible, as formulated,with other reactive ingredients. In relation to the use of ammoniumsalts, such salts can be simply admixed with the detergent compositionbut are prone to adsorb water and/or liberate ammonia during storage.Accordingly. such materials, if present, are desirably protected in aparticle such as that described in U.S. Pat. No. 4,652,392, Baginski etal.

Builders—Detergent builders selected from aluminosilicates and silicatesare preferably included in the compositions herein, for example toassist in controlling mineral, especially Ca and/or Mg, hardness in washwater or to assist in the removal of particulate soils from surfaces.

Suitable silicate builders include water-soluble and hydrous solid typesand including those having chain-, layer-, orthree-dimensional-structure as well as amorphous-solid ornon-structured-liquid types. Preferred are alkali metal silicates,particularly those liquids and solids having a SiO₂:Na₂O ratio in therange 1.6:1 to 3.2:1, including, particularly for automatic dishwashingpurposes, solid hydrous 2-ratio silicates marketed by PQ Corp. under thetradename BRITESIL®, e.g., BRITESIL H2O; and layered silicates, e.g.,those described in U.S. Pat. No. 4,664,839, May 12, 1987, H. P. Rieck.NaSKS-6. sometimes abbreviated “SKS-6”, is a crystalline layeredaluminum-free δ-Na₂SiO₅ morphology silicate marketed by Hoechst and ispreferred especially in granular laundry compositions. See preparativemethods in German DE-A-3,417,649 and DE-A-3,742,043. Other layeredsilicates, such as those having the general formulaNaMSi_(x)O_(2x+1).yH₂O wherein M is sodium or hydrogen, x is a numberfrom 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably0, can also or alternately be used herein. Layered silicates fromHoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the α, β and γlayer-silicate forms. Other silicates may also be useful, such asmagnesium silicate, which can serve as a crispening agent in granules,as a stabilizing agent for bleaches, and as a component of suds controlsystems.

Also suitable for use herein are synthesized crystalline ion exchangematerials or hydrates thereof having chain structure and a compositionrepresented by the following general formula in an anhydride form:xM₂O.ySiO₂.zM′O wherein M is Na and/or K, M′ is Ca and/or Mg; y/x is 0.5to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. Pat. No. 5,427,711,Sakaguchi et al, Jun. 27, 1995.

Aluminosilicate builders are especially useful in granular detergents,but can also be incorporated in liquids, pastes or gels. Suitable forthe present purposes are those having empirical formula:[M_(z)(AlO₂)_(z)(SiO₂)_(v)].xH₂O wherein z and v are integers of atleast 6, the molar ratio of z to v is in the range from 1.0 to 0.5, andx is an integer from 15 to 264. Aluminosilicates can be crystalline oramorphous, naturally-occurring or synthetically derived. Analuminosilicate production method is in U.S. Pat. No. 3,985,669,Krummel, et al, Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials are available as Zeolite A,Zeolite P (B), Zeolite X and, to whatever extent this differs fromZeolite P, the so-called Zeolite MAP. Natural types, includingclinoptilolite, may be used. Zeolite A has the formula:Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O wherein x is from 20 to 30, especially 27.Dehydrated zeolites (x=0-10) may also be used. Preferably, thealuminosilicate has a particle size of 0.1-10 microns in diameter.

Detergent builders in place of or in addition to the silicates andaluminosilicates described hereinbefore can optionally be included inthe compositions herein, for example to assist in controlling mineral,especially Ca and/or Mg, hardness in wash water or to assist in theremoval of particulate soils from surfaces. Builders can operate via avariety of mechanisms including forming soluble or insoluble complexeswith hardness ions, by ion exchange, and by offering a surface morefavorable to the precipitation of hardness ions than are the surfaces ofarticles to be cleaned. Builder level can vary widely depending upon enduse and physical form of the composition. Built detergents typicallycomprise at least about 1% builder. Liquid formulations typicallycomprise about 5% to about 50%, more typically 5% to 35% of builder.Granular formulations typically comprise from about 10% to about 80%,more typically 15% to 50% builder by weight of the detergentcomposition. Lower or higher levels of builders are not excluded. Forexample, certain detergent additive or high-surfactant formulations canbe unbuilt.

Suitable builders herein can be selected from the group consisting ofphosphates and polyphosphates, especially the sodium salts; carbonates,bicarbonates, sesquicarbonates and carbonate minerals other than sodiumcarbonate or sesquicarbonate; organic mono-, di-, trio, andtetracarboxylates especially water-soluble nonsurfactant carboxylates inacid, sodium, potassium or alkanolammonium salt form, as well asoligomeric or water-soluble low molecular weight polymer complemented byborates, e.g., for pH-buffering purposes, or by sulfates, especiallysodium sulfate and any other fillers or carriers which may be importantto the engineering of stable surfactant and/or builder-containingdetergent compositions.

Builder mixtures, sometimes termed “builder systems” can be used andtypically comprise two or more conventional builders, optionallycomplemented by chelants, pH-buffers or fillers, though these lattermaterials are generally accounted for separately when describingquantities of materials herein. In terms of relative quantities ofsurfactant and builder in the present detergents, preferred buildersystems are typically formulated at a weight ratio of surfactant tobuilder of from about 60:1 to about 1:80. Certain preferred laundrydetergents have said ratio in the range 0.90:1.0 to 4.0:1.0, morepreferably from 0.95:1.0 to 3.0:1.0.

P-containing detergent builders often preferred where permitted bylegislation include, but are not limited to, the alkali metal, ammoniumand alkanolammonium salts of polyphosphates exemplified by thetripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; andphosphonates.

Suitable carbonate builders include alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973, although sodium bicarbonate, sodiumcarbonate, sodium sesquicarbonate, and other carbonate minerals such astrona or any convenient multiple salts of sodium carbonate and calciumcarbonate such as those having the composition 2Na₂CO₃.CaCO₃ whenanhydrous, and even calcium carbonates including calcite, aragonite andvaterite, especially forms having high surface areas relative to compactcalcite may be useful, for example as seeds or for use in syntheticdetergent bars.

Suitable organic detergent builders include polycarboxylate compounds,including water-soluble nonsurfactant dicarboxylates andtricarboxylates. More typically builder polycarboxylates have aplurality of carboxylate groups, preferably at least 3 carboxylates.Carboxylate builders can be formulated in acid, partially neutral,neutral or overbased form. When in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.Polycarboxylate builders include the ether polycarboxylates, such asoxydisuccinate, see Berg, U.S. Pat. No. 3,128,287, Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, Jan. 18, 1972; “TMS/TDS”builders of U.S. Pat. No. 4,663,071. Bush et al, May 5, 1987; and otherether carboxylates including cyclic and alicyclic compounds, such asthose described in U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903.

Other suitable builders are the ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether;1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid;carboxymethyloxysuccinic acid; the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as mellitic acid,succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxy-methyloxysuccinic acid, and soluble salts thereof

Citrates, e.g., citric acid and soluble salts thereof are importantcarboxylate builders e.g., for heavy duty liquid detergents, due toavailability from renewable resources and biodegradability. Citrates canalso be used in granular compositions, especially in combination withzeolite and/or layered silicates. Oxydisuccinates are also especiallyuseful in such compositions and combinations.

Where permitted, and especially in the formulation of bars used forhand-laundering operations and in granular laundry compositions, alkalimetal phosphates such as sodium tripolyphosphates, sodium pyrophosphateand sodium orthophosphate can be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates, e.g.,those of U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and3,422,137 can also be used and may have desirable antiscalingproperties.

Certain detersive surfactants or their short-chain homologs also have abuilder action. For unambiguous formula accounting purposes, when theyhave surfactant capability, these materials are summed up as detersivesurfactants. Preferred types for builder functionality are illustratedby: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, Jan. 28, 1986. Succinic acidbuilders include the C₅-C₂₀ alkyl and alkenyl succinic acids and saltsthereof. Succinate builders also include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Lauryl-succinates are describedin European Patent Application 86200690.5/0,200,263, published Nov. 5,1986. Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions as surfactant/builder materials aloneor in combination with the aforementioned builders, especially citrateand/or the succinate builders, to provide additional builder activity.Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, Mar. 7, 1967. See also Diehl, U.S. Pat. No. 3,723,322.

Other types of inorganic builder materials which can be used have theformula (M_(x))_(i)Ca_(y)(CO₃)_(z) wherein x and i are integers from 1to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M_(i)are cations, at least one of which is a water-soluble, and the equationΣ_(i)=₁₋₁₅(x_(i) multiplied by the valence of M_(i))+2y=2z is satisfiedsuch that the formula has a neutral or “balanced” charge. These buildersare referred to herein as “Mineral Builders”. Waters of hydration oranions other than carbonate may be added provided that the overallcharge is balanced or neutral. The charge or valence effects of suchanions should be added to the right side of the above equation.Preferably, there is present a water-soluble cation selected from thegroup consisting of hydrogen, water-soluble metals, hydrogen, boron,ammonium, silicon, and mixtures thereof, more preferably, sodium,potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium andpotassium being highly preferred. Nonlimiting examples of noncarbonateanions include those selected from the group consisting of chloride,sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate,nitrate, borate and mixtures thereof. Preferred builders of this type intheir simplest forms are selected from the group consisting ofNa₂Ca(CO₃)₂, K₂Ca(CO₃)₂, Na₂Ca₂(CO₃)₃, NaKCa(CO₃)₂, NaKCa₂(CO₃)₃,K₂Ca₂(CO₃)₃, and combinations thereof. An especially preferred materialfor the builder described herein is Na₂Ca(CO₃)₂ in any of itscrystalline modifications. Suitable builders of the above-defined typeare further illustrated by, and include, the natural or synthetic formsof any one or combinations of the following minerals: Afghanite,Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite,Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY,Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite,Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettnerite,Khanneshite, LepersonniteGd, Liottite, MckelveyiteY, Microsommite,Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite,Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite,Vishnevite, and Zemkorite. Preferred mineral forms include Nyererite,Fairchildite and Shortite.

Detersive Surfactants:

The detergent compositions according to the present invention preferablyfurther comprise additional surfactants, herein also referred to asco-surfactants. It is to be understood that the surfactant systemsprepared in the manner of the present invention may be used singly incleaning compositions or in combination with other detersivesurfactants. Typically, fully-formulated cleaning compositions willcontain a mixture of surfactant types in order to obtain broad-scalecleaning performance over a variety of soils and stains and under avariety of usage conditions. One advantage of the branched-chainsurfactants herein is their ability to be readily formulated incombination with other known surfactant types. Nonlimiting examples ofadditional surfactants which may be used herein typically at levels fromabout 1% to about 55%, by weight, include the unsaturated sulfates suchas oleyl sulfate, the C₁₀-C₁₈ alkyl alkoxy sulfates (“AE_(x)S”;especially EO 1-7 ethoxy sulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates(especially the EO 1-5 ethoxycarboxylates), the C₁₀-C₁₈ glycerol ethersulfates, the C₁₀-C₁₈ alkyl polyglycosides and their correspondingsulfated polyglycosides, and C₁₂-C₁₈ alpha-sulfonated fatty acid esters.Nonionic surfactants such as the ethoxylated C₁₀-C₁₈ alcohols and alkylphenols, (e.g., C₁₀-C₁₈ EO (1-10) can also be used. If desired, otherconventional surfactants such as the C₁₂-C₁₈ betaines and sulfobetaines(“sultaines”), C₁₀-C₁₈ amine oxides, and the like, can also be includedin the overall compositions. The C₁₀-C₁₈ N-alkyl polyhydroxy fatty acidamides can also be used. Typical examples include the C₁₂-C₁₈N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactantsinclude the N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈glucamides can be used for low sudsing. C₁₀-C₂₀ conventional soaps mayalso be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆soaps may be used.

A wide range of these co-surfactants can be used in the detergentcompositions of the present invention. A typical listing of anionic,nonionic, ampholyic and zwitterionic classes, and species of theseco-surfactants, is given in U.S. Pat. No. 3,664,961 issued to Norris onMay 23, 1972. Amphoteric surfactants are also described in detail in“Amphoteric Surfactants, Second Edition”, E. G. Lomax, Editor (published1996, by Marcel Dekker, Inc.).

The laundry detergent compositions of the present invention typicallycomprise in total from about 0.1% to about 35%. preferably from about0.5% to about 15%, by weight of co-surfactants. Selected additionalco-surfactants are further identified as follows.

(1) Anionic Co-surfactants

Nonlimiting examples of anionic co-surfactants useful herein, typicallyat levels from about 0.1% to about 50%, by weight, include the primary,branched-chain and random C₁₀-C₂₀ alkyl sulfates (“AS”), the C₁₀-C₁₈secondary (2,3) alkyl sulfates of the formula CH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺)CH₃ and CH₃ (CH₂)_(y)(CHOSO₃ ⁻M⁺) CH₂CH₃ where x and (y+1) are integersof at least about 7, preferably at least about 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀-C₁₈ alpha-sulfonated fatty acid esters, theC₁₀-C₁₈ sulfated alkyl polyglycosides, the C₁₀-C₁₈ alkyl alkoxy sulfates(“AE_(x)S”; especially EO 1-7 ethoxy sulfates), and C₁₀-C₁₈ alkyl alkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates). The C₁₂-C₁₈betaines and sulfobetaines (“sultaines”), C₁₀-C₁₈ amine oxides, and thelike, can also be included in the overall compositions. C₁₀-C₂₀conventional soaps may also be used. If high sudsing is desired, thebranched-chain C₁₀-C₁₆ soaps may be used. Other conventional usefulanionic co-surfactants are listed in standard texts.

The alkyl alkoxy sulfate surfactants useful herein are preferably watersoluble salts or acids of the formula RO(A)_(m)SO₃M wherein R is anunsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄ alkylcomponent, preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, more preferablyC₁₂-C₁₅ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m isgreater than zero, typically between about 0.5 and about 6, morepreferably between about 0.5 and about 3, and M is H or a cation whichcan be, for example, a metal cation (e.g., sodium, potassium, lithium,calcium, magnesium, etc.), ammonium or substituted-ammonium cation.Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates arecontemplated herein. Specific examples of substituted ammonium cationsinclude ethanol-, triethanol-, methyl-, dimethyl, trimethyl-ammoniumcations and quaternary ammonium cations such as tetramethyl-ammonium anddimethyl piperidinium cations and those derived from alkylamines such asethylamine, diethylamine, triethylamine, mixtures thereof, and the like.Exemplary surfactants are C₁₂-C₁₅ alkyl polyethoxylate (1.0) sulfate(C₁₂-C₁₅E(1.0)M), C₁₂-C₁₅ alkyl polyethoxylate (2.25) sulfate(C₁₂-C₁₅E(2.25)M), C₁₂-C₁₅ alkyl polyethoxylate (3.0) sulfate(C₁₂-C₁₅E(3.0)M), and C₁₂-C₁₅ alkyl polyethoxylate (4.0) sulfate(C₁₂-C₁₅E(4.0)M), wherein M is conveniently selected from sodium andpotassium.

The alkyl sulfate surfactants useful herein are preferably water solublesalts or acids of the formula ROSO₃M wherein R preferably is a C₁₀-C₂₄hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀-C₁₈ alkylcomponent, more preferably a C₁₂-C₁₅ alkyl or hydroxyalkyl, and M is Hor a cation, e.g., an alkali metal cation (e.g. sodium, potassium,lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-,and trimethyl ammonium cations and quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperidinium cations and quaternaryammonium cations derived from alkylamines such as ethylamine,diethylamine, triethylamine, and mixtures thereof, and the like).

Other suitable anionic surfactants that can be used are alkyl estersulfonate surfactants including linear esters of C₈-C₂₀ carboxylic acids(i.e., fatty acids) which are sulfonated with gaseous SO₃ according to“The Journal of the American Oil Chemists Society”, 52 (1975), pp.323-329. Suitable starting materials would include natural fattysubstances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula:

R³—CH(SO₃M)—C(O)—OR⁴

wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alkyl, or combinationthereof, R⁴ is a C₁-C₆ hydrocarbyl, preferably an alkyl, or combinationthereof, and M is a cation which forms a water soluble salt with thealkyl ester sulfonate. Suitable salt-forming cations include metals suchas sodium, potassium, and lithium, and substituted or unsubstitutedammonium cations, such as monoethanolamine, diethanolamine, andtriethanolamine. Preferably, R³ is C₁₀-C₁₆ alkyl, and R⁴ is methyl,ethyl or isopropyl. Especially preferred are the methyl ester sulfonateswherein R³ is C₁₀-C₁₆ alkyl.

Other anionic co-surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present invention.These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di- andtriethanolamine salts) of soap, C₈-C₂₂ primary of secondaryalkanesulfonates, C₈-C₂₄ olefinsulfonates, sulfonated polycarboxylicacids prepared by sulfonation of the pyrolyzed product of alkaline earthmetal citrates, e.g., as described in British patent specification No.1,082,179, C₈-C₂₄ alkylpolyglycolethersulfates (containing up to 10moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerolsulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxideether sulfates, paraffin sulfonates, alkyl phosphates, isethionates suchas the acyl isethionates, N-acyl taurates, alkyl succinamates andsulfosuccinates, monoesters of sulfosuccinates (especially saturated andunsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates(especially saturated and unsaturated C₆-C₁₂ diesters), sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), and alkylpolyethoxy carboxylates such as those of the formulaRO(CH₂CH₂O)_(k)—CH₂COO—M+ wherein R is a C₈-C₂₂ alkyl, k is an integerfrom 0 to 10 and M is a soluble salt-forming cation. Resin acids andhydrogenated resin acids are also suitable, such as rosin, hydrogenatedrosin, and resin acids and hydrogenated resin acids present in orderived from tall oil. Further examples are described in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). Avariety of such surfactants are also generally disclosed in U.S. Pat.No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23,line 58 through Column 29, line 23 (herein incorporated by reference).

Another suitable anionic co-surfactant are the disulfates. Preferreddisulfate surfactants have the formula

where R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether,ester, amine or amide group of chain length C₁ to C₂₈, preferably C₃ toC₂₄, most preferably C₈ to C₂₀, or hydrogen; A and B are independentlyselected from alkyl, substituted alkyl, and alkenyl groups of chainlength C₁ to C₂₈, preferably C₁ to C₅, most preferably C₁ or C₂, or acovalent bond, and A and B in total contain at least 2 atoms; A, B, andR in total contain from 4 to about 31 carbon atoms; X and Y are anionicgroups selected from the group consisting of sulfate and sulfonate,provided that at least one of X or Y is a sulfate group; and M is acationic moiety, preferably a substituted or unsubstituted ammonium ion,or an alkali or alkaline earth metal ion.

The most preferred disulfate surfactant has the formula as above where Ris an alkyl group of chain length from C₁₀ to C₁₈, A and B areindependently C₁ or C₂, both X and Y are sulfate groups, and M is apotassium, ammonium, or a sodium ion. See U.S. patent application Ser.No. 08/882,217 filed Jun. 28, 1996, assigned to Procter & Gamble.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 0.1% to about 50%, preferablyfrom about 1% to about 40% by weight of an anionic surfactant.

(2) Nonionic Co-surfactants

Nonlimiting examples of nonionic co-surfactants useful herein typicallyat levels from about 0.1% to about 50%, by weight include thealkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acidamides (PFAA's), alkyl polyglycosides (APG's), C₁₀-C₁₈ glycerol ethers,and the like.

More specifically, the condensation products of primary and secondaryaliphatic alcohols with from about 1 to about 25 moles of ethylene oxide(AE) are suitable for use as the nonionic surfactant in the presentinvention. The alkyl chain of the aliphatic alcohol can either bestraight or branched, primary or secondary, and generally contains fromabout 8 to about 22 carbon atoms. Preferred are the condensationproducts of alcohols having an alkyl group containing from about 8 toabout 20 carbon atoms, more preferably from about 10 to about 18 carbonatoms, with from about 1 to about 10 moles, preferably 2 to 7, mostpreferably 2 to 5, of ethylene oxide per mole of alcohol. Especiallypreferred nonionic surfactants of this type are the C₉-C₁₅ primaryalcohol ethoxylates containing 3-12 moles of ethylene oxide per mole ofalcohol, particularly the C₁₂-C₁₅ primary alcohols containing 5-10 molesof ethylene oxide per mole of alcohol.

Examples of commercially available nonionic surfactants of this typeinclude: Tergitol™ 15-S-9 (the condensation product of C₁₁-C₁₅ linearalcohol with 9 moles ethylene oxide) and Tergitol™ 24-L-6 NMW (thecondensation product of C₁₂-C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol™ 45-9 (the condensation product ofC₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3(the condensation product of C₁₂-C₁₃ linear alcohol with 3 moles ofethylene oxide), Neodol™ 45-7 (the condensation product of C₁₄-C₁₅linear alcohol with 7 moles of ethylene oxide) and Neodol™ 45-5 (thecondensation product of C₁₄-C₁₅ linear alcohol with 5 moles of ethyleneoxide) marketed by Shell Chemical Company; Kyro™ EOB (the condensationproduct of C₁₃-C₁₅ alcohol with 9 moles ethylene oxide), marketed by TheProcter & Gamble Company; and Genapol LA O3O or O5O (the condensationproduct of C₁₂-C₁₄ alcohol with 3 or 5 moles of ethylene oxide) marketedby Hoechst. The preferred range of HLB in these AE nonionic surfactantsis from 8-17 and most preferred from 8-14. Condensates with propyleneoxide and butylene oxides may also be used.

Another class of preferred nonionic co-surfactants for use herein arethe polyhydroxy fatty acid amide surfactants of the formula.

wherein R¹ is H, or C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propylor a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Preferably, R¹ is methyl. R² is a straight C₁₁₋₁₅ alkyl orC₁₅₋₁₇ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,and Z is derived from a reducing sugar such as glucose, fructose,maltose, lactose, in a reductive amination reaction. Typical examplesinclude the C₁₂-C₁₈ and C₁₂-C₁₄ N-methylglucamides. See U.S. Pat. Nos.5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can alsobe used, see U.S. Pat. No. 5,489,393.

Also useful as a nonionic co-surfactant in the present invention are thealkylpolysaccharides such as those disclosed in U.S. Pat. No. 4,565,647,Llenado, issued Jan. 21, 1986, having a hydrophobic group containingfrom about 6 to about 30 carbon atoms, preferably from about 10 to about16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilicgroup containing from about 1.3 to about 10, preferably from about 1.3to about 3, most preferably from about 1.3 to about 2.7 saccharideunits. Any reducing saccharide containing 5 or 6 carbon atoms can beused, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties (optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside). The intersaccharidebonds can be, e.g., between the one position of the additionalsaccharide units and the 2-, 3-, 4-, and/or 6-positions on the precedingsaccharide units.

Preferred alkylpolyglycosides have the formula

R²O(C_(n)H_(2n)O)_(t)(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.Compounds of this type and their use in detergent are disclosed in EP-B0 070 077, 0 075 996 and 0 094 118.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are also suitable for use as the nonionic surfactant of thesurfactant systems of the present invention, with the polyethylene oxidecondensates being preferred. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to about 14 carbon atoms, preferably from about 8 to about 14 carbonatoms, in either a straight-chain or branched-chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 2 to about 25 moles, morepreferably from about 3 to about 15 moles, of ethylene oxide per mole ofalkyl phenol. Commercially available nonionic surfactants of this typeinclude Igepal™ CO-630, marketed by the GAF Corporation; and Triton™X-45, X-114. X-100 and X-102, all marketed by the Rohm & Haas Company.These surfactants are commonly referred to as alkylphenol alkoxylates(e.g., alkyl phenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol arealso suitable for use as the additional nonionic surfactant in thepresent invention. The hydrophobic portion of these compounds willpreferably have a molecular weight of from about 1500 to about 1800 andwill exhibit water insolubility. The addition of polyoxyethylenemoieties to this hydrophobic portion tends to increase the watersolubility of the molecule as a whole, and the liquid character of theproduct is retained up to the point where the polyoxyethylene content isabout 50% of the total weight of the condensation product, whichcorresponds to condensation with up to about 40 moles of ethylene oxide.Examples of compounds of this type include certain of thecommercially-available Pluronic™ surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionicsurfactant system of the present invention, are the condensationproducts of ethylene oxide with the product resulting from the reactionof propylene oxide and ethylenediamine. The hydrophobic moiety of theseproducts consists of the reaction product of ethylenediamine and excesspropylene oxide, and generally has a molecular weight of from about 2500to about 3000. This hydrophobic moiety is condensed with ethylene oxideto the extent that the condensation product contains from about 40% toabout 80% by weight of polyoxyethylene and has a molecular weight offrom about 5,000 to about 11,000. Examples of this type of nonionicsurfactant include certain of the commercially available Tetronic™compounds, marketed by BASF.

Also preferred nonionics are amine oxide surfactants. The compositionsof the present invention may comprise amine oxide in accordance with thegeneral formula I:

R¹(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O  (I).

In general, it can be seen that the structure (I) provides onelong-chain moiety R¹(EO)_(x)(PO)_(y)(BO)_(z) and two short chainmoieties, CH₂R′. R′ is preferably selected from hydrogen, methyl and—CH₂OH. In general R¹ is a primary or branched hydrocarbyl moiety whichcan be saturated or unsaturated, preferably, R¹ is a primary alkylmoiety. When x+y+z=0, R¹ is a hydrocarbyl moiety having chainlength offrom about 8 to about 18. When x+y+z is different from 0, R¹ may besomewhat longer, having a chainlength in the range C₁₂-C₂₄. The generalformula also encompasses amine oxides wherein x+y+z=0, R₁=C₈-C₁₈, R′=Hand q=0-2, preferably 2. These amine oxides are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamineoxide and their hydrates, especially the dihydrates as disclosed in U.S.Pat. Nos. 5,075,501 and 5,071,594, incorporated herein by reference.

The invention also encompasses amine oxides wherein x+y+z is differentfrom zero, specifically x+y+z is from about 1 to about 10, R¹ is aprimary alkyl group containing 8 to about 24 carbons, preferably fromabout 12 to about 16 carbon atoms; in these embodiments y+z ispreferably 0 and x is preferably from about 1 to about 6, morepreferably from about 2 to about 4; EO represents ethyleneoxy; POrepresents propyleneoxy; and BO represents butyleneoxy. Such amineoxides can be prepared by conventional synthetic methods, e.g., by thereaction of alkylethoxysulfates with dimethylamine followed by oxidationof the ethoxylated amine with hydrogen peroxide.

Highly preferred amine oxides herein are solutions at ambienttemperature. Amine oxides suitable for use herein are made commerciallyby a number of suppliers, including Akzo Chemie, Ethyl Corp., andProcter & Gamble. See McCutcheon's compilation and Kirk-Othmer reviewarticle for alternate amine oxide manufacturers.

Whereas in certain of the preferred embodiments R′ is H, there is somelatitude with respect to having R′ slightly larger than H. Specifically,the invention further encompasses embodiments wherein R′ is CHOH, suchas hexadecylbis(2-hydroxyethyl)amine oxide,tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amineoxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamineoxide dihydrate.

Polymeric Soil Release Agent—The compositions according to the presentinvention may optionally comprise one or more soil release agents.Polymeric soil release agents are characterized by having bothhydrophilic segments, to hydrophilize the surface of hydrophobic fibers,such as polyester and nylon, and hydrophobic segments, to deposit uponhydrophobic fibers and remain adhered thereto through completion of thelaundry cycle and, thus, serve as an anchor for the hydrophilicsegments. This can enable stains occurring subsequent to treatment withthe soil release agent to be more easily cleaned in later washingprocedures.

If utilized, soil release agents will generally comprise from about0.01% to about 10% preferably from about 0.1% to about 5%, morepreferably from about 0.2% to about 3% by weight, of the composition.

The following, all included herein by reference, describe soil releasepolymers suitable for us in the present invention. U.S. Pat. No.5,691,298 Gosselink et al., issued Nov. 25, 1997; U.S. Pat. No.5,599,782 Pan et al., issued Feb. 4, 1997; U.S. Pat. No. 5,415,807Gosselink et al., issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrallet al., issued Jan. 26, 1993; U.S. Pat. No. 4,956,447 Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 4,976,879 Maldonado et al. issuedDec. 11, 1990; U.S. Pat. No. 4,968,451 Scheibel et al., issued Nov. 6,1990; U.S. Pat. No. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;U.S. Pat. No. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. No.4,877,896 Maldonado et al., issued Oct. 31, 1989; U.S. Pat. No.4,702,857 Gosselink et al., issued Oct. 27, 1987; U.S. Pat. No.4,711,730 Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580Gosselink issued Jan. 26, 1988; U.S. Pat. No. 4,000,093 Nicol et al.,issued Dec. 28, 1976; U.S. Pat. No. 3,959,230 Hayes, issued May 25,1976; U.S. Pat. No. 3,893,929 Basadur, issued Jul. 8, 1975; and EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824 Voilland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681 Ruppert et al.;U.S. Pat. Nos. 4,220,918; 4,787,989; EP 279,134 A, 1988 to Rhone-PoulencChemie; EP 457,205 A to BASF (1991); and DE 2,335,044 to Unilever N. V.,1974; all incorporated herein by reference.

Clay Soil Removal/Anti-redeposition Agents—The compositions of thepresent invention can also optionally contain water-soluble ethoxylatedamines having clay soil removal and antiredeposition properties.Granular detergent compositions which contain these compounds typicallycontain from about 0.01% to about 10.0% by weight of the water-solubleethoxylates amines; liquid detergent compositions typically containabout 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. See U.S. Pat. No. 4,891,160, VanderMeer, issuedJan. 2, 1990 and WO 95/32272, published Nov. 30, 1995. Another type ofpreferred antiredeposition agent includes the carboxy methyl cellulose(CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents—Polymeric dispersing agents canadvantageously be utilized at levels from about 0.1% to about 7%, byweight, in the compositions herein, especially in the presence ofzeolite and/or layered silicate builders. Suitable polymeric dispersingagents include polymeric polycarboxylates and polyethylene glycols,although others known in the art can also be used. It is believed,though it is not intended to be limited by theory, that polymericdispersing agents enhance overall detergent builder performance, whenused in combination with other builders (including lower molecularweight polycarboxylates) by crystal growth inhibition, particulate soilrelease peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in European Patent Application No.66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep.3, 1986, which also describes such polymers comprisinghydroxypropylacrylate. Still other useful dispersing agents include themaleic/acrylie/vinyl alcohol terpolymers. Such materials are alsodisclosed in EP 193,360, including, for example, the 45/45/10 terpolymerof acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Brightener—Any optical brighteners or other brightening or whiteningagents known in the art can be incorporated at levels typically fromabout 0.01% to about 1.2%, by weight, into the detergent compositionsherein. Commercial optical brighteners which may be useful in thepresent invention can be classified into subgroups, which include, butare not necessarily limited to, derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines,dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ringheterocycles, and other miscellaneous agents. Examples of suchbrighteners are disclosed in “The Production and Application ofFluorescent Brightening Agents”, M. Zahradnik, Published by John Wiley &Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13. 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, the2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles;4,4′-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4′-bis(styryl)bisphenyls; andthe amino-coumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene;1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-styryl-naptho[1,2-d]oxazole; and2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton.

Dye Transfer Inhibiting Agents—The compositions of the present inventionmay also include one or more materials effective for inhibiting thetransfer of dyes from one fabric to another during the cleaning process.Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-manganese phthalocyanine, peroxidases,and mixtures thereof. If used, these agents typically comprise fromabout 0.01% to about 10% by weight of the composition, preferably fromabout 0.01% to about 5%, and more preferably from about 0.05% to about2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R—A_(x)—P;wherein P is a polymerizable unit to which an N—O group can be attachedor the N—O group can form part of the polymerizable unit or the N—Ogroup can be attached to both units; A is one of the followingstructures: —NC(O)—, —C(O)O—, —S—, —O—, —N═; x is 0 or 1; and R isaliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclicgroups or any combination thereof to which the nitrogen of the N—O groupcan be attached or the N—O group is part of these groups. Preferredpolyamine N-oxides are those wherein R is a heterocyclic group such aspyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivativesthereof.

The N—O group can be represented by the following general structures:

wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic or alicyclicgroups or combinations thereof, x, y and z are 0 or 1; and the nitrogenof the N—O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa<10, preferably pKa<7, more preferred pKa<6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as “PVNO”.

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as “PVPVI”) are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113.“Modern Methods of Polymer Characterization”, the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinylpyrrolidone (“PVP”) having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol (“PEG”)having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from about 0.01%to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

When in the above formula, R¹ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory, it is believed that such brighteners work this waybecause they have high affinity for fabrics in the wash solution andtherefore deposit relatively quick on these fabrics. The extent to whichbrighteners deposit on fabrics in the wash solution can be defined by aparameter called the “exhaustion coefficient”. The exhaustioncoefficient is in general as the ratio of a) the brightener materialdeposited on fabric to b) the initial brightener concentration in thewash liquor. Brighteners with relatively high exhaustion coefficientsare the most suitable for inhibiting dye transfer in the context of thepresent invention.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds can optionally be used in the presentcompositions to provide conventional fabric “brightness” benefits,rather than a true dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Chelating Agents—The detergent compositions herein may also optionallycontain one or more iron and/or manganese chelating agents. Suchchelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures therein, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotri-acetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

If utilized, these chelating agents will generally comprise from about0.1% to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Suds Suppressors—Compounds for reducing or suppressing the formation ofsuds can be incorporated into the compositions of the present invention.Suds suppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos. 4,489,455and 4,489,574 and in front-loading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep.27, 1960 to Wayne St. John. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitablesalts include the alkali metal salts such as sodium, potassium, andlithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphaticC₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range ofabout −40° C. and about 50° C., and a minimum boiling point not lessthan about 110° C. (atmospheric pressure). It is also known to utilizewaxy hydrocarbons, preferably having a melting point below about 100° C.The hydrocarbons constitute a preferred category of suds suppressor fordetergent compositions. Hydrocarbon suds suppressors are described, forexample, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo etal. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, andheterocyclic saturated or unsaturated hydrocarbons having from about 12to about 70 carbon atoms. The term “paraffin,” as used in this sudssuppressor discussion, is intended to include mixtures of true paraffinsand cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing amount of a suds controlling agent consisting essentiallyof:

(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs.to about 1,500 cs. at 25° C.;

(ii) from about 5 to about 50 parts per 100 parts by weight of (i) ofsiloxane resin composed of (CH₃)₃SiO/_(1/2) units of SiO₂ units in aratio of from (CH₃)₃ SiO_(1/2) units and to SiO₂ units of from about0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of asolid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergentcompositions with controlled suds will optionally comprise from about0.001 to about 1, preferably from about 0.01 to about 0.7, mostpreferably from about 0.05 to about 0.5, weight % of said silicone sudssuppressor, which comprises (1) a nonaqueous emulsion of a primaryantifoam agent which is a mixture of (a) a polyorganosiloxane, (b) aresinous siloxane or a silicone resin-producing silicone compound, (c) afinely divided filler material, and (d) a catalyst to promote thereaction of mixture components (a), (b) and (c), to form silanolates;(2) at least one nonionic silicone surfactant; and (3) polyethyleneglycol or a copolymer of polyethylene-polypropylene glycol having asolubility in water at room temperature of more than about 2 weight %;and without polypropylene glycol. Similar amounts can be used ingranular compositions, gels, etc. See also U.S. Pat. No. 4,978,471,Starch, issued Dec. 18, 1990, and U.S. Pat. No. 4,983,316, Starch,issued Jan. 8, 1991, U.S. Pat. No. 5,288,431, Huber et al., issued Feb.22, 1994, and U.S. Pat. Nos. 4,639,489 and 4,749,740, Aizawa et al atcolumn 1, line 46 through column 4, line 35.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than about 1,000, preferablybetween about 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than about 2 weight %, preferably more thanabout 5 weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than about 1,000, more preferably between about100 and 800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between about 1:1 and 1:10, mostpreferably between 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679,4,075,118 and EP 150,872. The secondary alcohols include the C₆-C₁₆alkyl alcohols having a C₁-C₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademarkISALCHEM 123 from Enichem. Mixed suds suppressors typically comprisemixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a “suds suppressing amount. By “suds suppressing amount” is meantthat the formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines.

The compositions herein will generally comprise from 0% to about 10% ofsuds suppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts therein, will be present typically in amounts up toabout 5%, by weight, of the detergent composition. Preferably, fromabout 0.5% to about 3% of fatty monocarboxylate suds suppressor isutilized. Silicone suds suppressors are typically utilized in amounts upto about 2.0%, by weight, of the detergent composition, although higheramounts may be used. This upper limit is practical in nature, dueprimarily to concern with keeping costs minimized and effectiveness oflower amounts for effectively controlling sudsing. Preferably from about0.01% to about 1% of silicone suds suppressor is used, more preferablyfrom about 0.25% to about 0.5%. As used herein, these weight percentagevalues include any silica that may be utilized in combination withpolyorganosiloxane, as well as any adjunct materials that may beutilized. Monostearyl phosphate suds suppressors are generally utilizedin amounts ranging from about 0.1% to about 2%, by weight, of thecomposition. Hydrocarbon suds suppressors are typically utilized inamounts ranging from about 0.01% to about 5.0%, although higher levelscan be used. The alcohol suds suppressors are typically used at 0.2%-3%by weight of the finished compositions.

Alkoxylated Polycarboxylates—Alkoxylated polycarboxylates such as thoseprepared from polyacrylates are useful herein to provide additionalgrease removal performance. Such materials are described in WO 91/08281and PCT 90/01815 at p. 4 et seq., incorporated herein by reference.Chemically, these materials comprise polyacrylates having one ethoxyside-chain per every 7-8 acrylate units. The side-chains are of theformula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. Theside-chains are ester-linked to the polyacrylate “backbone” to provide a“comb” polymer type structure. The molecular weight can vary, but istypically in the range of about 2000 to about 50,000. Such alkoxylatedpolycarboxylates can comprise from about 0.05% to about 10%, by weight,of the compositions herein.

Fabric Softeners—Various through-the-wash fabric softeners, especiallythe impalpable smectite clays of U.S. Pat. No. 4,062,647, Storm andNirschl, issued Dec. 13, 1977, as well as other softener clays known inthe art, can optionally be used typically at levels of from about 0.5%to about 10% by weight in the present compositions to provide fabricsoftener benefits concurrently with fabric cleaning. Clay softeners canbe used in combination with amine and cationic softeners as disclosed,for example, in U.S. Pat. No. 4,375,416. Crisp et al, Mar. 1, 1983 andU.S. Pat. No. 4,291,071, Harris et al, issued Sep. 22, 1981.

Perfumes—Perfumes and perfumery ingredients useful in the presentcompositions and processes comprise a wide variety of natural andsynthetic chemical ingredients, including, but not limited to,aldehydes, ketones, esters, and the like. Also included are variousnatural extracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes typically comprise from about 0.01%to about 2%, by weight, of the detergent compositions herein, andindividual perfumery ingredients can comprise from about 0.0001% toabout 90% of a finished perfume composition.

Non-limiting examples of perfume ingredients useful herein include:7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;ionone methyl; ionone gamma methyl; methyl cedrylone; methyldihydrojasmonate, methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; fortnyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane; beta-naphthol methyl ether;ambroxane; dodecahydro-3a,6,6,9a-tetra-methylnaphtho[2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those that provide thelargest odor improvements in finished product compositions containingcellulases. These perfumes include but are not limited to: hexylcinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethyinaphtho[2,1b]furan; anisalde-hyde;coumarin; cedrol; vanillin, cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resinsfrom a variety of sources including, but not limited to: Peru balsam,Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoinresin, coriander and lavandin. Still other perfume chemicals includephenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol,nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, andeugenol. Carriers such as diethylphthalate can be used in the finishedperfume compositions.

Other Ingredients—A wide variety of other ingredients useful indetergent compositions can be included in the compositions herein,including other active ingredients, carriers, hydrotropes, processingaids, dyes or pigments, solvents for liquid formulations, solid fillersfor bar compositions etc. If high sudsing is desired, suds boosters suchas the C₁₀-C₁₆ alkanolamides can be incorporated into the compositions,typically at 1%-10% levels. The C₁₀-C₁₄ monoethanol and diethanol amidesillustrate a typical class of such suds boosters. Use of such sudsboosters with high sudsing adjunct surfactants such as the amine oxides,betaines and sultaines noted above is also advantageous. If desired,water-soluble magnesium and/or calcium salts such as MgC₂, MgSO₄, CaCl₂,CaSO₄ and the like, can be added at levels of, typically, 0.1%-2%, toprovide additional suds and to enhance grease removal performance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5×the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500-12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned enzymes, bleaches, bleach activators, bleachcatalysts, photoactivators, dyes, fluorescers, fabric conditioners andhydrolyzable surfactants can be “protected” for use in detergents,including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5%to 90%, typically 10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, preferably between about7.5 and 10.5. Liquid dishwashing product formulations preferably have apH between about 6.8 and about 9.0. Laundry products are typically at pH9-11. Techniques for controlling pH at recommended usage levels includethe use of buffers, alkalis, acids, etc., and are well known to thoseskilled in the art.

Form of the Compositions

The compositions in accordance with the invention can take a variety ofphysical forms including granular, tablet, bar and liquid forms. Thecompositions are particularly the so-called concentrated granulardetergent compositions adapted to be added to a washing machine by meansof a dispensing device placed in the machine drum with the soiled fabricload.

The mean particle size of the components of granular compositions inaccordance with the invention should preferably be such that no morethat 5% of particles are greater than 1.7 mm in diameter and not morethan 5% of particles are less than 0.1 5 mm in diameter.

The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of Tyler sieves. The weight fractions therebyobtained are plotted against the aperture size of the sieves. The meanparticle size is taken to be the aperture size through which 50% byweight of the sample would pass.

The bulk density of granular detergent compositions in accordance withthe present invention typically have a bulk density of at least 600g/liter, more preferably from 650 g/liter to 1200 g/liter. Bulk densityis measured by means of a simple funnel and cup device consisting of aconical funnel moulded rigidly on a base and provided with a flap valveat its lower extremity to allow the contents of the funnel to be emptiedinto an axially aligned cylindrical cup disposed below the funnel. Thefunnel is 130 mm high and has internal diameters of 130 mm and 40 mm atits respective upper and lower extremities. It is mounted so that thelower extremity is 140 mm above the upper surface of the base. The cuphas an overall height of 90 mm, an internal height of 87 mm and aninternal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by handpouring, the flap valve is opened and powder allowed to overfill thecup. The filled cup is removed from the frame and excess powder removedfrom the cup by passing a straight edged implement e.g., a knife, acrossits upper edge. The filled cup is then weighed and the value obtainedfor the weight of powder doubled to provide a bulk density in g/liter.Replicate measurements are made as required.

Surfactant System Agglomerate Particles

The surfactant system herein is preferably present in granularcompositions in the form of agglomerate particles, which may take theform of flakes, prills, marumes, noodles, ribbons, but preferably takethe form of granules. The most preferred way to process the particles isby agglomerating powders (e.g. aluminosilicate, carbonate) with highactive mid-chain branched primary alkyl sulfate pastes and to controlthe particle size of the resultant agglomerates within specified limits.Such a process involves mixing an effective amount of powder with a highactive mid-chain branched primary alkyl sulfate paste in one or moreagglomerators such as a pan agglomerator, a Z-blade mixer or morepreferably an in-line mixer such as those manufactured by Schugi(Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, andGebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse7-9, Postfach 2050. Germany. Most preferably a high shear mixer is used,such as a Lodige CB (Trade Name).

A high active mid-chain branched primary alkyl sulfate paste comprisingfrom 50% by weight to 95% by weight, preferably 70% by weight to 85% byweight of mid-chain branched primary alkyl sulfate is typically used.The paste may be pumped into the agglomerator at a temperature highenough to maintain a pumpable viscosity, but low enough to avoiddegradation of the surfactants used. An operating temperature of thepaste of 50° C. to 80° C. is typical.

Laundry Washing Method

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 20 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65liters, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

As noted, the surfactant system are used herein in detergentcompositions, preferably in combination with other detersivesurfactants, at levels which are effective for achieving at least adirectional improvement in cleaning performance. In the context of afabric laundry composition, such “usage levels” can vary depending notonly on the type and severity of the soils and stains, but also on thewash water temperature, the volume of wash water and the type of washingmachine.

As can be seen from the foregoing, the amount of mid-chain branchedprimary alkyl sulfate surfactant used in a machine-wash launderingcontext can vary, depending on the habits and practices of the user, thetype of washing machine, and the like.

In a preferred use aspect a dispensing device is employed in the washingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash cycle. Its volume capacityshould be such as to be able to contain sufficient detergent product aswould normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensingdevice containing the detergent product is placed inside the drum. Atthe commencement of the wash cycle of the washing machine water isintroduced into the drum and the drum periodically rotates. The designof the dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product duringthe wash cycle in response to its agitation as the drum rotates and alsoas a result of its contact with the wash water.

To allow for release of the detergent product during the wash the devicemay possess a number of openings through which the product may pass.Alternatively, the device may be made of a material which is permeableto liquid but impermeable to the solid product, which will allow releaseof dissolved product. Preferably, the detergent product will be rapidlyreleased at the start of the wash cycle thereby providing transientlocalised high concentrations of product in the drum of the washingmachine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a waythat container integrity is maintained in both the dry state and duringthe wash cycle. Especially preferred dispensing devices for use with thecomposition of the invention have been described in the followingpatents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345and EP-A-0288346. An article by J. Bland published in ManufacturingChemist, Nov. 1989, pages 41-46 also describes especially preferreddispensing devices for use with granular laundry products which are of atype commonly know as the “granulette”. Another preferred dispensingdevice for use with the compositions of this invention is disclosed inPCT Patent Application No. W094/11562.

Especially preferred dispensing devices are disclosed in European PatentApplication Publication Nos. 0343069 & 0343070. The latter Applicationdiscloses a device comprising a flexible sheath in the form of a bagextending from a support ring defining an orifice, the orifice beingadapted to admit to the bag sufficient product for one washing cycle ina washing process. A portion of the washing medium flows through theorifice into the bag, dissolves the product, and the solution thenpasses outwardly through the orifice into the washing medium. Thesupport ring is provided with a masking arrangement to prevent egress ofwetted, undissolved, product, this arrangement typically comprisingradially extending walls extending from a central boss in a spoked wheelconfiguration, or a similar structure in which the walls have a helicalform.

Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated with awater impermeable protective material so as to retain the contents, suchas is disclosed in European published Patent Application No. 0018678.Alternatively it may be formed of a water-insoluble synthetic polymericmaterial provided with an edge seal or closure designed to rupture inaqueous media as disclosed in European published Patent Application Nos.0011500, 0011501, 0011502, and 0011968. A convenient form of waterfrangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric filmsuch as polyethylene or polypropylene.

Machine Dishwashing Method

Any suitable methods for machine washing or cleaning soiled tableware,particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 liters,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

Packaging for the Compositions

Commercially marketed executions of the bleaching compositions can bepackaged in any suitable container including those constructed frompaper, cardboard, plastic materials and any suitable laminates. Apreferred packaging execution is described in European Application No.94921505.7.

In the following Examples, the abbreviations for the various ingredientsused for the compositions have the following meanings.

LAS Sodium linear C₁₂ alkyl benzene sulfonate MBAS_(x) Mid-chainbranched primary alkyl (average total carbons = x) sulfate LMFAA C12-14alkyl N-methyl glucamide APA C8-C10 amido propyl dimethyl amine FattyAcid C12-C14 fatty acid (C12/14) Fatty Acid (TPK) Topped palm kernelfatty acid Fatty Acid (RPS) Rapeseed fatty acid Borax Na tetraboratedecahydrate PAA Polyacrylic Acid (mw = 4500) PBG Polyethylene glycol (mw= 4600) MES Alkyl methyl ester sulfonate SAS Secondary alkyl sulfateNaPS Sodium paraffin sulfonate C45AS Sodium C₁₄-C₁₅ linear alkyl sulfateCxyEzS Sodium C_(1x)-C_(1y) alkyl sulfate condensed with z moles ofethylene oxide CxyEz A C_(1x-1y) branched primary alcohol condensed withan average of z moles of ethylene oxide QAS Ethoquad C/12 orR₂.N⁺(CH₃)₂(C₂H₄OH) with R₂ = C₁₂-C₁₄ TFAA C₁₆-C₁₈ alkyl N-methylglucamide STPP Anhydrous sodium tripolyphosphate Zeolite A HydratedSodium Aluminosilicate of formula Na₁₂(AlO₂SiO₂)₁₂.27H₂O having aprimary particle size in the range from 0.1 to 10 micrometers NaSKS-6Crystalline layered silicate of formula δ-Na₂Si₂O₅ Carbonate Anhydroussodium carbonate with a particle size between 200 μm and 900 μmBicarbonate Anhydrous sodium bicarbonate with a particle sizedistribution between 400 μm and 1200 μm Silicate Amorphous SodiumSilicate (SiO₂:Na₂O; 2.0 ratio) Sodium sulfate Anhydrous sodium sulfateMA/AA Copolymer of 1:4 maleic/acrylic acid, average molecular weightabout 70,000. CMC Sodium carboxymethyl cellulose Protease Proteolyticenzyme of activity 4 KNPU/g sold by NOVO Industries A/S under thetradename Savinase Cellulase Cellulytic enzyme of activity 1000 CEVU/gsold by NOVO Industries A/S under the tradename Carezyme AmylaseAmylolytic enzyme of activity 60 KNU/g sold by NOVO Industries A/S underthe tradename Termamyl 60T Lipase Lipolytic enzyme of activity 100 kLU/gsold by NOVO Industries A/S under the tradename Lipolase PB4 Sodiumperborate tetrahydrate of nominal formula NaBO₂.3H₂O.H₂O₂ PB1 Anhydroussodium perborate bleach of nominal formula NaBO₂.H₂O₂ PercarbonateSodium Percarbonate of nominal formula 2Na₂CO₃.3H₂O₂ NaDCC Sodiumdichloroisocyanurate NOBS Nonanoyloxybenzene sulfonate in the form ofthe sodium salt. TAED Tetraacetylethylenediamine DTPMP Diethylenetriamine penta (methylene phosphonate), marketed by Monsanto under theTrade name Dequest 2060 Photoactivated Sulfonated Zinc Phthlocyanineencapsulated in bleach dextrin soluble polymer Brightener 1 Disodium4,4′-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium4,4′-bis(4-anilino-6-morpholino-1.3.5- triazin-2-yl)amino)stilbene-2:2′-disulfonate. HEDP 1,1-hydroxyethane diphosphonic acid SRP1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloylbackbone Silicone Polydimethylsiloxane foam controller with siloxane-antifoam oxyalkylene copolymer as dispersing agent with a ratio of saidfoam controller to said dispersing agent of 10:1 to 100:1. DTPADiethylene triamine pentaacetic acid

In the following Examples all levels are quoted as % by weight of thecomposition. The following examples are illustrative of the presentinvention, but are not meant to limit or otherwise define its scope. Allparts, percentages and ratios used herein are expressed as percentweight unless otherwise specified.

EXAMPLE 1

The following laundry detergent compositions A to D are prepared inaccord with the invention:

A B C D MBAS 11 14 11 8 (avg. total carbons = 16.5) C12 LAS 11 8 11 14Any Combination of: 1 0 0 0 C45 AS C45E1S C16 SAS C14-17 NaPS C14-18 MESEthoquad C/12 1 1 1 1 C23E6.5 1.5 1.5 1.5 1.5 Zeolite A 27.8 27.8 27.827.8 PAA 2.3 2.3 2.3 2.3 Carbonate 27.3 27.3 27.3 27.3 Silicate 0.6 0.60.6 0.6 Perborate 1.0 1.0 1.0 1.0 Protease 0.3 0.3 0.3 0.3 Carezyme 0.30.3 0.3 0.3 SRP 0.4 0.4 0.4 0.4 Brightener 0.2 0.2 0.2 0.2 PEG 1.6 1.61.6 1.6 Sulfate 5.5 5.5 5.5 5.5 Silicone Antifoam 0.42 0.42 0.42 0.42Moisture & Minors - - - Balance - - -

EXAMPLE 2

The following laundry detergent compositions E to F are prepared inaccord with the invention:

E F G H I MBAS 8.2 8.2 10.5 8.2 6.2 (avg. total carbons = 16.5) C11.8LAS 8.2 8.2 6 8.2 14 QAS 0.5 1 2 2 2 TFAA 1.6 0 0 0 0 C24E3 4.9 4.9 4.94.9 4.9 Zeolite A 15 15 15 15 15 NaSKS-6 11 11 11 11 11 Citrate 3 3 3 33 MA/AA 4.8 4.8 4.8 4.8 4.8 HEDP 0.5 0.5 0.5 0.5 0.5 Carbonate 8.5 8.58.5 8.5 8.5 Percarbonate 20.7 20.7 20.7 20.7 20.7 TAED 4.8 4.8 4.8 4.84.8 Protease 0.9 0.9 0.9 0.9 0.9 Lipase 0.15 0.15 0.15 0.15 0.15Carezyme 0.26 0.26 0.26 0.26 0.26 Amylase 0.36 0.36 0.36 0.36 0.36 SRP0.2 0.2 0.2 0.2 0.2 Brightener 0.2 0.2 0.2 0.2 0.2 Sulfate 2.3 2.3 2.32.3 2.3 Silicone Antifoam 0.4 0.4 0.4 0.4 0.4 Moisture & Minors - - -Balance - - - Density (g/L) 850 850 850 850

EXAMPLE 3

The following laundry detergent compositions J to O are prepared inaccord with the invention:

J K L M N O MBAS 16 16 20.5 16 16 11.5 (avg. total carbons = 16.5) C12LAS 16 16 11.5 16 16 20.5 Any Com- 2 4 0 0 0 0 bination of: C45 AS C45E1C16 SAS C14-17 NaPS C14-18 MES C23E6.5 3.6 3.6 3.6 3.6 3.6 3.6 QAS 1 1 11 2 1 Zeolite A 9.0 9.0 9.0 9.0 9.0 9.0 Poly- 7.0 7.0 7.0 7.0 7.0 7.0carboxylate Carbonate 18.4 18.4 18.4 18.4 18.4 18.4 Silicate 11.3 11.311.3 11.3 11.3 11.3 Perborate 3.9 3.9 3.9 3.9 3.9 3.9 NOBS 4.1 4.1 4.14.1 4.1 4.1 Protease 0.9 0.9 0.9 0.9 0.9 0.9 SRP 0.5 0.5 0.5 0.5 0.5 0.5Brightener 0.3 0.3 0.3 0.3 0.3 0.3 PEG 0.2 0.2 0.2 0.2 0.2 0.2 Sulfate5.1 5.1 5.1 5.1 5.1 5.1 Silicone 0.2 0.2 0.2 0.2 0.2 0.2 AntifoamMoisture & - - - Balance - - - Minors Density (g/L) 810 810 810 810 810810

EXAMPLE 4

The following laundry detergent compositions O to Q are prepared inaccord with the invention:

O P Q MBAS (avg. total carbons = 16.5) 14 11 8 C12 LAS 8 11 14 QAS 0.5 11.5 C23E6.5 1.2 1.2 1.2 STPP 35.0 35.0 35.0 Carbonate 19.0 19.0 19.0Zeolite A 16.0 16.0 16.0 Silicate 2.0 2.0 2.0 CMC 0.3 0.3 0.3 Protease1.4 1.4 1.4 Lipolase 0.12 0.12 0.12 SRP 0.3 0.3 0.3 Brightener 0.2 0.20.2 Moisture & Minors - - - Balance - - -

EXAMPLE 5

Sodium salts of branched sulfated surfactants are made by reaction ofthe appropriate branched alcohols with chlorosulfonic acid in ethylether. The resulting acid is neutralized with a stoichiometric amount ofsodium methoxide in methanol and the solvents are evaporated via vacuumoven. The branched alcohols are made from linear olefins (alpha and/orinternal olefins) that have been molecularly re-arranged by exposure toappropriate catalysts. No additional carbons are added in thisre-arrangement, but the starting olefin is isomerized so that it nowcontains one or more alkyl branches along the main alkyl chain. As theolefin moiety stays intact throughout this molecular re-arrangement,a—CH₂OH group is then added via hydroformylation chemistry. Thefollowing Shell Research experimental test alcohol samples are sulfated.

¹³C-NMR Results For Branched Alcohols Prepared Total Number of Carbons16 17 18 Avg. Number of Branches per Molecule 2.0 1.7 2.1 Average BranchPosition Relative To Hydroxyl Carbon % at C4 and higher 56% 55% 52% % atC3 26% 21% 25% % at C2 18% 24% 23% Type of Branching % propyl and higher31% 35% 30% % ethyl 12% 10% 12% % methyl 57% 55% 58%

Solutions of laundry prototype formulas are prepared as shown below.

R S T C12 LAS 10.6 10.6 10.6 C23E6.5 1.5 1.5 1.5 C15 branched sulfate,sodium salt — — 10.6 C16 branched sulfate, sodium salt 10.6 — — C17branched sulfate, sodium salt — 10.6 — QAS 1 1 1 Zeolite A 27 27 27Carbonate 5 5 5 Sulfate 5 5 5 Perborate 1 1 1 Polyacrylic Acid (MW =4500) 2 2 2 Polyethylene Glycol (MW 4600) 0.9 0.9 0.9 Silicate 0.6 0.60.6 Moisture & Miscellaneous - - - Balance - - -

U V W LAS 14 14 14 C45 AS 2.4 2.4 2.4 C45E1S 0.9 0.9 0.9 C23E6.5 1.5 1.51.5 C16 branched sulfate, sodium salt 8.0 — — C17 branched sulfate,sodium salt — 8.0 4.0 C18 branched sulfate, sodium salt — — 4.0 QAS 1.51.5 1.5 Zeolite A 26 26 26 Carbonate 19.3 19.3 19.3 Sulfate 5 5 5Perborate 1 1 1 Polyacrylic Acid (MW = 4500) 2 2 2 Polyethylene Glycol(MW = 4600) 0.9 0.9 0.9 Silicate 0.6 0.6 0.6 Water - - - Balance - - -

EXAMPLE 6

The following high density detergent formulations, according to thepresent invention, are prepared:

X Y Z Agglomerate C12 LAS 9 7 5 MBAS 5 7 9 QAS 1 1 1 Zeolite A 15.0 15.015.0 Carbonate 4.0 4.0 4.0 MA/AA 4.0 4.0 4.0 CMC 0.5 0.5 0.5 DTPMP 0.40.4 0.4 Spray On C25E5 5.0 5.0 5.0 Perfume 0.5 0.5 0.5 Dry Adds C45AS6.0 6.0 3.0 HEDP 0.5 0.5 0.5 SKS-6 13.0 13.0 13.0 Citrate 3.0 3.0 3.0TAED 5.0 5.0 5.0 Percarbonate 20.0 20.0 20.0 SRP 1 0.3 0.3 0.3 Protease1.4 1.4 1.4 Lipase 0.4 0.4 0.4 Cellulase 0.6 0.6 0.6 Amylase 0.6 0.6 0.6Silicone antifoam 5.0 5.0 5.0 Brightener 1 0.2 0.2 0.2 Brightener 2 0.20.2 0.2 Balance (Moisture and Miscellaneous) 100 100 100 Density(g/liter) 850 850 850

EXAMPLE 7

The following liquid laundry detergent compositions AA to CC areprepared in accord with the invention:

AA BB CC MBAS (14.5-15.5 ave. total carbon) 7.5 11 14 C11.3 LAS 14 117.5 QAS 1 1 1 LMFAA 2.5-3.5 2.5-3.5 2.5-3.5 C23E9 0.6-2   0.6-2  0.6-2   APA   0-0.5   0-0.5   0-0.5 Citric Acid 3.0 3.0 3.0 Fatty Acid(TPK or C12/14) 2.0 2.0 2.0 Ethanol 3.4 3.4 3.4 Propanediol 6.4 6.4 6.4Monoethanol amine 1.0 1.0 1.0 NaOH 3.0 3.0 3.0 Na toluene sulfonate 2.32.3 2.3 Na formate 0.1 0.1 0.1 Borax   2-2.5 2-2.5 2-2.5 Protease 0.90.9 0.9 Lipase 0.04-0.08 0.04-0.08 0.04-0.08 Amylase 0.15 0.15 0.15Cellulase 0.05 0.05 0.05 Ethoxylated TEPA 1.2 1.2 1.2 SRP 2 0.1-0.20.1-0.2 0.1-0.2 Brightener 3 0.15 0.15 0.15 Silicone antifoam 0.12 0.120.12 Fumed Silica 0.0015 0.0015 0.0015 Perfume 0.3 0.3 0.3 Dye 0.00130.00123 0.0013 Moisture/minors Balance Balance Balance Product pH (10%in DI water) 7.7 7.7 7.7

EXAMPLE 8

The following liquid laundry detergent compositions DD to FF areprepared in accord with the invention:

DD EE FF MBAS (14.5-15.5 ave. total carbon) 13 10 7 C11.3 LAS 7 10 13Any combination of: 1 1 1 C25 AExS*Na (x = 1.8-2.5) C25 AS (linear tohigh 2-alkyl) C14-17 NaPS C12-16 SAS C18 1,4 disuifate C12-16 MES QAS 11 1 LMFAA 3.5-5.5 3.5-5.5 3.5-5.5 C23E9 4-6 4-6 4-6 APA   0-1.5   0-1.5  0-1.5 Citric Acid 1 1 1 Fatty Acid (TPK or C12/14) 7.5 7.5 7.5 FattyAcid (Rapeseed) 3.1 3.1 3.1 Ethanol 1.8 1.8 1.8 Propanediol 9.4 9.4 9.4Monoethanol amine 6.5 6.5 6.5 NaOH 1.5 1.5 1.5 Na toluene sulfonate 0-20-2 0-2 Borate (in ionic form)   2-2.5   2-2.5   2-2.5 CaCl2 0.02 0.020.02 Protease 0.48-0.6  0.48-0.6  0.48-0.6  Lipase 0.06-0.14 0.06-0.140.06-0.14 Amylase 0.06-0.14 0.06-0.14 0.06-0.14 Cellulase 0.03 0.03 0.03Ethoxylated TEPA 0.2-0.7 0.2-0.7 0.2-0.7 SRP 3 0.1-0.2 0.1-0.2 0.1-0.2Brightener 4 0.15 0.15 0.15 Silicone antifoam  0.2-0.25  0.2-0.25 0.2-0.25 Isofol 16 0-2 0-2 0-2 Fumed Silica 0.0015 0.0015 0.0015Perfume 0.5 0.5 0.5 Dye 0.0013 0.0013 0.0013 Moisture/minors BalanceBalance Balance Product pH (10% in DI water) 7.6 7.6 7.6

What is claimed is:
 1. Cleaning compositions comprising surfactantsystems which comprise: (a) from 80% to 99%, by weight of an anioniccosurfactant mixture of mid-chain branched primary alkyl sulfates andlinear alkyl benzene sulfonates, wherein said mixture comprises: (i)from 35% to 80%, by weight of this anionic cosurfactant mixture, ofmid-chain branched primary alkyl sulfates having the formula:

 wherein the total number of carbon atoms in the branched primary alkylmoiety of this formula, including the R, R¹, and R² branching, is from14 to 20, and wherein further for this surfactant mixture the averagetotal number of carbon atoms in the branched primary alkyl moietieshaving the above formula is within the range of greater than 14.5 to 18,R, R¹, and R² are each independently selected from hydrogen and C₁-C₃alkyl, provided R, R¹, and R² are not all hydrogen and, when z is 1, atleast R or R¹ is not hydrogen; M is one or more cations; w is an integerfrom 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to13; z is an integer of at least 1; and w+x+y+z is from 8 to 14; and (ii)from 20% to 65%, by weight of this anionic cosurfactant mixture, ofC₁₀-C₁₆ linear alkyl benzene sulfonate; and (b) from 1% to 20%, byweight of one or more cationic cosurfactants.
 2. A composition accordingto claim 1 wherein at least 0.001%, by weight of the mixture comprisesone or more mid-chain branched primary alkyl sulfates having theformula:

wherein the total number of carbon atoms, including branching, is from15 to 18, and wherein further for this surfactant mixture the averagetotal number of carbon atoms in the branched primary alkyl moietieshaving the above formula is within the range of greater than 14.5 to 18;R¹ and R² are each independently hydrogen or C₁-C₃ alkyl; M is a watersoluble cation; x is from 0 to 11; y is from 0 to 11; z is at least 2;and x+y+z is from 9 to 13; provided R¹ and R² are not both hydrogen. 3.A composition according to claim 1 wherein M is selected from the groupconsisting of sodium, potassium, calcium, magnesium, quaternary alkylamines having the formula

wherein R³, R⁴, R⁵ and R⁶ are independently selected from hydrogen,C₁-C₆ alkylene, C₄-C₆ branched alkylene, C₁-C₆ alkanol, C₁-C₆alkenylene, C₄-C₆ branched alkenylene, and mixtures thereof.
 4. Acomposition according to claim 1 wherein M is sodium, potassium, andmixtures thereof.
 5. A composition according to claim 1 wherein at least5%, by weight of the mixture comprises one or more mid-chain branchedprimary alkyl sulfates wherein x+y is equal to 9 and z is equal to
 2. 6.A composition according to of claim 1 wherein at least 5%, by weight ofthe mixture comprises mid-chain branched primary alkyl sulfates whereinx+y is equal to 9 and z is equal to
 2. 7. A composition according toclaim 1 wherein at least 5%, by weight of the mixture comprisesmid-chain branched primary alkyl sulfates wherein x+y is equal to 10 andz is equal to
 2. 8. Cleaning compositions comprising: (1) from about0.1% to about 99.9% by weight of a surfactant system, wherein saidsurfactant system comprises: (a) from about 80% to about 99%, by weightof an anionic cosurfactant mixture of mid-chain branched primary alkylsulfates and linear alkyl benzene sulfonates, wherein said mixturecomprises: (i) from about 35% to about 80%, by weight of this anioniccosurfactant mixture, of mid-chain branched primary alkyl sulfateshaving the formula:

 wherein the total number of carbon atoms per molecule, includingbranching, is from 14 to 20, and wherein further for this surfactantmixture the average total number of carbon atoms in the branched primaryalkyl moieties having the above formula is within the range of greaterthan 14.5 to about 18; R, R¹, and R² are each independently selectedfrom hydrogen and C₁-C₃ alkyl, provided R, R¹, and R² are not allhydrogen; M is a water soluble cation; w is an integer from 0 to 13; xis an integer from 0 to 13; y is an integer from 0 to 13; z is aninteger of at least 1; and w+x+y+z is from 8 to 14; provided that whenR² is a C₁-C₃ alkyl the ratio of surfactants having z equal to 1 tosurfactants having z of 2 or greater is at least about 1:1, and (ii)from about 20% to about 65%, by weight of this anionic cosurfactantmixture, of C₁₀-C₁₆ linear alkyl benzene sulfonate; and (b) from about1% to about 20%, by weight of one or more cationic cosurfactants; and(2) from about 0.1% to about 99.9% by weight of one or more cleaningcomposition adjunct ingredients.
 9. A cleaning composition according toclaim 8 wherein the amount of branched surfactants, when R² is a C₁-C₃alkyl, comprises less than about 20%, by weight of branched primaryalkyl sulfates having the above formula wherein z equals
 1. 10. Acleaning composition according to claim 1 comprising a mixture ofmid-chain branched primary alkyl sulfate surfactants wherein saidmixture comprises at least about 5% by weight of two or more mid-chainbranched alkyl sulfates having the formula:

or mixtures thereof; wherein M represents one or more cations; a, b, d,and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 andwherein further when a+b=10, a is an integer from 2 to 9 and b is aninteger from 1 to 8; when a+b=11, a is an integer from 2 to 10 and b isan integer from 1 to 9; when a+b=12, a is an integer from 2 to 11 and bis an integer from 1 to 10; when a+b=13, a is an integer from 2 to 12and b is an integer from 1 to 11; when a+b=14, a is an integer from 2 to13 and b is an integer from 1 to 12; when a+b=15, a is an integer from 2to 14 and b is an integer from 1 to 13; when a+b=16, a is an integerfrom 2 to 15 and b is an integer from 1 to 14; when d+e=8, d is aninteger from 2 to 7 and e is an integer from 1 to 6; when d+e=9, d is aninteger from 2 to 8 and e is an integer from 1 to 7; when d+e=10, d isan integer from 2 to 9 and e is an integer from 1 to 8; when d+e=11, dis an integer from 2 to 10 and e is an integer from 1 to 9; when d+e=12,d is an integer from 2 to 11 and e is an integer from 1 to 10; whend+e=13, d is an integer from 2 to 12 and e is an integer from 1 to 11;when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to12; wherein for this surfactant mixture the average total number ofcarbon atoms in the branched primary alkyl moieties having the aboveformulas is within the range of greater than 14.5 to about
 18. 11. Acleaning composition according to claim 1 wherein the mid-chain branchedprimary alkyl sulfate comprises one or more mono-methyl branched primaryalkyl sulfates selected from the group consisting of: 3-methylpentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methylpentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methylpentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methylpentadecanol sulfate, 10-methyl pentadecanol sulfate, 11-methylpentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methylpentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanolsulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate,7-methyl hexadecanol sulfate, 8-methyl hexadecanol sulfate, 9-methylhexadecanol sulfate, 10-methyl hexadecanol sulfate, 11-methylhexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-methylhexadecanol sulfate, 14-methyl hexadecanol sulfate, and mixturesthereof.
 12. A cleaning composition according to claim 1 wherein themid-chain branched primary alkyl sulfate comprises one or more di-methylbranched primary alkyl sulfates selected from the group consisting of:2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate,2,5-methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate,2,7-methyl tetradecanol sulfate, 2,8-methyl tetradecanol sulfate,2,9-methyl tetradecanol sulfate, 2,10-methyl tetradecanol sulfate,2,11-methyl tetradecanol sulfate, 2,12-methyl tetradecanol sulfate,2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate,2,5-methyl pentadecanol sulfate, 2,6-methyl pentadecanol sulfate,2,7-methyl pentadecanol sulfate, 2,8-methyl pentadecanol sulfate,2,9-methyl pentadecanol sulfate, 2,10-methyl pentadecanol sulfate,2,11-methyl pentadecanol sulfate, 2,12-methyl pentadecanol sulfate,2,13-methyl pentadecanol sulfate, and mixtures thereof.
 13. A method forcleaning fabrics, said method comprising contacting a fabric in need ofcleaning with an aqueous solution of a cleaning composition according toclaim
 1. 14. A cleaning composition according to claim 1 wherein saidcationic cosurfactant is selected from the group consisting of:

wherein R₁ is a C₅-C₃₁ linear or branched alkyl, alkenyl or alkarylchain or M⁻.N⁺(R₆R₇R₈)(CH₂)_(s); X and Y, independently, are selectedfrom the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONHand NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH orNHCOO group; R₂, R₃, R₄, R₆, R₇ and R₈ are independently selected fromthe group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl andalkaryl groups having from 1 to 4 carbon atoms; and R₅ is independentlyH or a C₁-C₃ alkyl group; wherein the values of m, n, s and tindependently lie in the range of from 0 to 8, the value of b lies inthe range from 0 to 20, and the values of a, u and v independently areeither 0 or 1 with the proviso that at least one of u or v must be 1;and wherein M is a counter anion;

wherein R¹ is a linear or branched alkyl or alkenyl moiety containingfrom about 8 to about 18 carbon atoms; R² is an alkyl group containingfrom one to three carbon atoms; R³ and R⁴ can vary independently and areselected from hydrogen methyl and ethyl; X⁻ is an anion sufficient toprovide electrical neutrality; A and A′ can vary independently and areeach selected from C₁-C₄ alkoxy, propoxy, butoxy and mixedethoxy/propoxy; p is from 0 to about 30; and (c) mixtures of (a) and(b).
 15. A cleaning composition according to claim 8 wherein saidcleaning composition adjunct ingredients are selected from the groupconsisting of, surfactants, builders, alkalinity system, organicpolymeric compounds, suds suppressors, soil suspension andanti-redeposition agents, corrosion inhibitor, bleaching agents, bleachactivators, bleach catalysts, enzymes, dye transfer inhibiting agents,brightener, chelants, perfume, hydrotropes, suds boosters, solvents andmixtures thereof.
 16. A cleaning composition according to claim 1wherein said composition is in the form of a granule, tablet, bar orliquid.